This sub has a lot of Napoleon experts but while you're waiting for them to reply I do have "Napoleon the great" by Andrew Roberts beside me so i'll give a start. It's important to first define what kind of mistakes you are comparing to each other and how to assess their value or lack there of. For example how can we assess his repeated mistakes of placing family upon the thrones of his defeated enemies despite he himself arguing they are incompetent and cause him nothing but trouble. Should we consider the battle of Trafalgar which he didn't directly command but which destroyed an chance of sea power, AND is that even a mistake or was it just simply a defeat, what is the difference? Napoleon is quoted to believe that we should "Never interfere with your enemy when he is making a mistake". So does a mistake exist if no-one takes advantage of it?

The main "mistakes" I think we should consider against the Russian campaign are: "The continental system", The Iberian Campaign, The Egyptian campaign, the planned invasion of England. I also think you could argue for Waterloo and Leipzig. I also think his repeated placing of trust in Talleyrand over and over again deserves a honorable mention.

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The continental system:

Whether it was good in theory can be debated but in reality it was a failure. Made in the Berlin decrees of 1806 these tariffs and the attempts to enforce them would lead him to the invasion of Portugal and the Iberian campaign in the belief that until the British ally Portugal joined the system it couldn't work (yeah...Portugal was why it didn't work..).

The Russian campaign which we are comparing against can also be seen as merely stemming from these tariffs as Napoleon was angry Russia was not enforcing them seriously. But this is the difficulty in evaluating such events as considering Russia had got off lightly so lightly after Tilsit (thanks to a belief that a friendship and common interest was struck between himself and the tsar) they had repaid Napoleon poorly and despite the Erfurt Convention meaning they should aid France against Austria, the Tsar managed to sent 70,000 troops who moved so slowly that by the time the campaign was over they only had 2 causalities. So while the continental system can be blamed as the mistake that led to the Russia Campaign we could also say that it would probably happen anyway.

This mistake did lead to Frances economy taking a hit, especially the strong middle class base which supported Napoleon, it also antagonized Britain (what ever chance they had of calling a truce was certainly diminished), his allies and pretty much all of Europe. The fact is it didn't work but hurt his economy, increased smuggling and actually LED to Britains balance being positive for the first time since 1780 and led them to diversify into Asia, Africa and elsewhere. An example of this failure is that the Grand Armee had to buy its shoes, greatcoats and vests from British manufacturers while paying for special licences to led them through the blockade.

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Chapter 20 - Iberia begins his Spanish campaign quoting him with "That unfortunate war destroyed me; it divided my forces, multiplied my obligations, undermined morale...All the circumstances of my disasters are bound in that fatal knot".

So Napoleon himself seems to believe that here lies his greatest mistake. Originally a weakly ruled "ally" that with both helped Napoleon in the disastrous battle of Trafalgar, and invasion of Portugal, Napoleons attempt at a take over (or liberation..) never went well or easy and the "Spanish ulcer" meant he had to waste 406,000 troops in a region that never gained him anything. It spread his forces, supply lines and wasted troops but it also led to defeats (though not when he was in command) and greatly damaged the invincible mystique of his grand armee. It also gave the a certain British officer Arthur Wellesley (later known as Wellington) practice and victory. I believe it can be argued that Spain was the beginning of the end as a slow and insidious poison which continually drained France after losing an ally. All in all this was a hell of a mistake.

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The Egyptian campaign:

Lesser known, it is perhaps best known for leading to the discovery of the Rosetta stone which was then captured by the British during the French expedition surrender. It is doubly funny that the British got the stone as Napoleon aimed to capture Egypt to control the Mediterranean and the Suez to block (well slow down) the British sea route to India. Some great propaganda led to this campaign being celebrated and Napoleon left Egypt to go become consul. A common mistake of Napoleon was to overestimate his strength at sea (the behemoth was no leviathan) and so Nelson destroyed his fleet and left the armee stranded on foreign soil to later completely surrender.

So how do we judge this? Napoleon said it was a victory and got the praise but in reality it was a total defeat, his navy destroyed, his army surrendered and his original plan was way to grand and nowhere realistic. Was it a mistake if it became his stepping stone?

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The English land invasion:

This is not just to be a smart ass. I truly believe this should be regarded as one of Napoleons biggest mistakes and that the only reason it inst is because he got saved by losing the battle of Trafalgar. This wasnt just a vague idea, he had detailed plans and camped his army ready to go right up to the campaign which led to the victory at Austerlitz. He had his ships were actively preparing for the transfer. If his fleet hadn't been destroyed at Trafalgar he was going to attempt this campaign (and even after this he still had plans to rebuild his fleet) and led me say this, he would have lost. The foraging skills of the army would struggle if England just pulled a mini Russia and took their people and food in any direction away from where Napoleon landed. Even if he landed there was no way he could keep his supply chains constantly up against the British navy and once they cut him from the mainland he would be on a timer. There are only so many people you can disembark at a time and amphibious landings are infamously difficult and dangerous led alone in the number he would need. Just a hundred small things added together would have led to it being seen as one of the greatest military blunders in history and he didn't lose it because he was never given the chance.

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I've written way too much so hopefully you found some of it interesting.