Simon Bolivar started admiring Napoleon as the very embodiment of Revolutionary success and virtue, but would later grow to resent him as an hypocrite who had betrayed his own principles in order to seize power for himself.
Bolivar was in his famous European tour when Napoleon crowned himself. These were important years for Bolivar. The love of his life, María Teresa, had died of malaria after he had brought her home to Venezuela. Heartbroken, Bolivar went to Europe, were he became a full-fledged revolutionary who dreamed of liberating Spanish America. The Little Corporal's military talent had given way to a golden age for France, which Bolivar, a young radical, contrasted with the decadence he had observed in Spain. That's when Bolivar made an oath to liberate Venezuela or die trying on the Monte Sacro, where the Roman plebs had rebelled against the Patricians.
Bolivar took this oath, justly enshrined as one of Venezuela's most important moments, some weeks after he and his tutor, Simon Rodriguez, a fellow radical, "saw Napoleon in person, a defining moment in the life of Bolívar". Bolivar was struck by "the emperor’s plain clothing in contrast to that of his officers". Bolivar's admiration had been betrayed some months earlier when Napoleon crowned himself as Emperor of the French. Different versions exist of Bolivar's reaction, and since Bolivar himself is a controversial person it would be difficult to know which one is true. The only constant is that Bolivar was repulsed by the action, but whether this disgust was accompanied by awe or not is contested.
O'Leary, Bolivar's aide de camp and a personal friend who remained loyal to him through thick and thin, claims that Bolivar was invited to the coronation but was so disgusted that he stayed in his house the entire day. Henceforth, Napoleon was not admired by Bolivar anymore, he was no longer "the symbol of liberty and glory, the object of his political admiration" but a simple tyrant. I should note that towards the end of his life Bolivar was often accused of trying to become another Napoleon, and some of the architects of Gran Colombia's dissolution such as General Paez supported this plan. Consequently, it's possible that O'Leary was just trying to defend Bolivar's reputation by asserting that Bolivar was horrified at Napoleon's crowning and thus would be even more horrified at the prospect of following his example. For what's it worth, Bolivar rejected Paez's schemes.
The Frenchman Peru de la Croix was similarly sympathetic to Bolivar, fighting as one of his generals and then being a die-hard supported who was even present as Bolivar died in exile. Nonetheless, in a diary entry written before he had become so loyal to Bolivar, de la Croix says that Bolivar was impressed by the love and admiration the French held for Napoleon, declaring that "The crown which Napoleon placed on his head I regarded as a miserable thing and a gothic fancy: what seemed great to me was the universal acclaim and interest that his person inspired. This, I confess, made me think of my country’s slavery and the glory in store for the man who would free her." This paints Bolivar more as a man hungry for power and glory, which contrasts the romantic and selfless revolutionary of O'Leary.
Napoleon is one of the main causes of the Spanish American revolutions, for the Juntas that propped up all over the continent supposedly did so to defend the colonies from Napoleon's clutches until the good king Fernando, deposed by Napoleon, could return. A Mexican patriot even exalted Napoleon by saying that "to you Spanish America owes the liberty and independence it now enjoys. Your sword struck the first blow at the chain which bound the two worlds." This was never Napoleon's aim, as he hoped the colonies would submit to the puppet regime he had created in Madrid. As the revolution started in Caracas, people who did not support King Fernando were called afrancesados (that is, influenced by France). Bolivar was one of them, both for his admiration of the achievements of the French Revolution, and also by his reckless support for complete independence. For the time being, the colonies wore "the mask of Fernando", pledging loyalty to the King when in truth they were asking for self-government and, eventually, independence.
Many years passed as Bolivar fought tirelessly for independence. Though he was too young to remember the aftermath of the Revolution of 1789, Bolivar was still impressed by how much France had advanced (Gran Colombia based its new organization and laws on France for example). It seems that his foremost inspiration remained the American Revolution, which most revolutionaries, notably Francisco de Miranda, regarded as more civilized and virtuous, free of the excesses that characterized the Terror. Bolivar himself really admired Washington, who was not stained by hypocrisy since he had remained a republican and had retired to live as a peaceful farmer. Bolivar wanted, to some extent, to be the Venezuelan Washington, and for the rest of his life he insisted that he did not want power and was just serving his people out of an ardent love for independence. This he contrasted with how Napoleon had betrayed the Revolution and sought to consolidate himself as the sole power in France. Still, Bolivar insisted that Gran Colombia had to become its own nation, and that it could not follow either France's example (protesting "I am not Napoleon, and Colombia is not France.") or the USA's (saying of Colombia's more restrained democracy "This is the code we must consult, not the code of Washington.").
When Napoleon fell from power, Bolivar was actually afraid he would flee to the Americas. If he fled to the United States, Bolivar thought Europe would declare war on them. But he was more afraid of him fleeing to South America, exclaiming that Colombia would be "forever dishonored" if it "received him with friendliness". Bolivar continued, declaring that Napoleon's "thirst for conquest" could not be quenched, faulting him for the "death of Europe's flower of youth", and expressing fear of Napoleon taking advantage of South America's problems to create another Empire at the cost of "what blood remains in our veins". Still, it seems that even at that point Bolivar still admired the man, at least a little, for in a letter he wrote in French to a friend he regarded Napoleon as "l'homme de l'immensité" (an immense, or towering, man) and one can infer that Bolivar knew just how influential Napoleon had been for he described Waterloo as a battle that would decide the destiny of the world.
After he had secured the independence of South America, and while he was travelling to Upper Peru (modern-day Bolivia) through the Andes, Bolivar forlornly admitted that he was envious of Napoleon's triumphal entry through the Alps, which he had seen in person. This suggests that Bolivar was jealous that Napoleon, despite being a traitor to the Republican principles Bolivar so cherished, had succeeded to make France a Great Nation whereas Gran Colombia was floundering under post-war devastation and political troubles. When Paez suggested Bolivar declare himself a monarch in order to unite Gran Colombia, he was insulted, saying that he was not led by "vulgar ambition" and that his title of Libertador was "superior to any that human pride can bestow. . . . I tell you frankly that this plan is not good for you, for me, or for the country." It's rather ironic that Bolivar was so against the idea of becoming a monarch, since at the same time he was pushing for the constitution he had written to be adopted by Colombia, a constitution that included a President for life that could designate his successor.
Bolivar's Gran Colombia failed, and at the end of his life he was not glorified and loved by the people he had liberated, but was hated by many. The Liberator met an ignominious end, dying a pathetic dead at the small island of Santa Marta. There is no record of his thoughts about Napoleon at that moment, but based on the great bitterness he expressed towards the Colombians and the people who had dismantled his experiment, one can assume that he was bitter or at the very least disappointed that he had not equaled the glory of the great heroes of modernity - which, naturally, included Napoleon. Summarizing, Bolivar at first admired Napoleon as a great Revolutionary hero, a virtuous Republican he wished to imitate in his own quest to liberate his homeland, but Bolivar grew profoundly disappointed after Napoleon crowned himself, and started to consider him a petty tyrant who had betrayed the Revolution.
Unfortunately, I don't know enough of Napoleon to tell you what he thought of Bolivar. None of my sources mention him expressing any opinion about Bolivar, which is natural since they all focus on Bolivar or Latin America. If he thought something of this upstart revolutionary, it may have been annoyance as Napoleon had hoped the Spanish colonies would submit to him, but as I said I'm not really sure.
Sources:
The Santander Regime in Gran Colombia, by David Bushnell.
Simon Bolivar, a Life, by John Lynch.
The Cambridge History of Latin America, by Leslie Bethell.
Americanos, Latin America's Struggle for Independence, by John Chasteen.