You have to understand that De Gaulle wasn't a natural leader for France, he was a WW1 veteran and a respected man (actually one of Pétain's protégés) but he was despised by other military leaders for his ideas on how to conduct warfaire (we were all about reinforcing defensive positions, the Maginot line and trench warfare, he wanted tanks and rapid maneuvers, something our ennemies did actually understand)

When WW2 broke out, he won a few battles but he was only a junior member of the government and a brigadier general when he fled to London, he was the de facto leader of the Free France only because he was the only cabinet member to be outside France at the time.

It caused a few problems with Churchill, Roosevelt and Staline who kinda acknowledged that he was the leader of the French Resistance and French Free Forces but didn't want him as the official representative of France after the war.

Hell, Roosevelt didn't even want to acknowledge the government of exile and wanted to rule France as a conquered territory after the war. Roosevelt also tried to appoint Henri Giraud as France's leader (he was more ... hmm, let's say eager to help the US and its interests) and forced De Gaulle to work with him, it only failed because all the Resistance movements and the French soldiers looked up to DG and saw him as their actual leader.

You can see why De Gaulle didn't really like his new "allies", he even said :

Never the Anglo-Saxons really treated us as real allies. They never consulted us, government to government, on any of their provisions. For political purpose or by convenience, they sought to use the French forces for their own goals, as if these forces belonged to them, alleging that they had provided weapons to them [...] I considered that I had to play the French game, since the others were playing theirs ... I deliberately adopted a stiffened and hardened attitude ...

The UK and the US had been hostile towards him during WW2 and didn't seem to take France interests into consideration when they planned the post-war era so he simply fought for his own country's interests and pushed away those who had only been allies of circumstances.

There were also 30+ attempts on the life of DG during his presidency, some that could be traced back to the NATO headquarters (and one where the CIA or the FBI might have been a co-conspirator) so you can understand why he left the whole organization.

De Gaulle's opposition to the British is often attributed to simple Anglophobia, an example of latter-day French dislike of "La perfide Albion". This position is supported by readings of De Gaulle's public speeches or reference to his relationship with his Allied comrades during the War, which could be euphemistically described as "turbulent". A particularly infamous, though fake, quotation of De Gaulle's in these scepter'd isles is "We shall stun [the British] with our ingratitude!"

To this theory, De Gaulle's main concern was Britain's "special relationship" with the United States and a fear that Britain would, as America's Trojan Horse, undermine the European project.

However, when I was researching to answer your question, I came across a convincing paper from one Andrew Moravcsik of Harvard, which I thought quite convincingly demonstrates that it was economic and commercial, rather than geopolitical concerns or anti-British racism that drove De Gaulle's veto of British EEC entry. For instance, in the press conference that announced De Gaulle's 2nd veto, he talked almost exclusively about economics.. Among other things, De Gaulle cited:

• British entry would undermine European and British agricultural policy, as the British, an island nation, would refuse to subsidize continental farmers in favor of cheaper Commonwealth produce, whilst continental producers would be hammered by such refusals.

• Unanimous opposition from French industrialists and farmers, such as the FNSEA and the CNPF.

• A free trade area would put the French economy, with its mal-valued franc and unmodernized industry, under strain for little reward.

• The Commission had said the British economy was incompatible with the common market.

• Britain had had to go cap-in-hand to the IMF in 1961 to prop up the pound, which underwent devaluation in 1949 and 1967, as well as suffering value crises in 61, 64, and 66.

• Britain had been forced to impose exchange controls to help the pound.

• Generally, it was a "monumental exception" to the Community's economy and would lead to chaos.

Moravcsik also points out that De Gaulle was not doing or saying anything his predecessors had not; he did not start French skepticism over Britain-in-Europe, and it was his protege and successor Georges Pompidou who helped to end it.

The truth is De Gaulle's stated reasons for his anti-British policies were all to do with commerce. The whole "anti-British" thing strikes me as a Little Englander coping mechanism: "he's just a typical duplicitous and ungrateful Frenchman with a chip on his shoulder". And the hostility was never one way - De Gaulle's first attempt to create a postwar European order was to advocate the breakup of Germany, which he was refused, and after that he proposed nuclear cooperation with the British and Americans - and was turned down. Franco-German led European integration was his last resort, not his first. De Gaulle and France had sound economic reasons to oppose British membership, and there is scant evidence that Anglophobia was a driver of De Gaulle's policy - indeed, these seem to rely on selective readings of De Gaulle's speeches, or imaginative extrapolations from a handful of private writings and anecdotes.

If you want to understand De Gaulle - Moravcsik's paper is excellent. He totally explodes the myth of De Gaulle as a bitter and Anglophobic "typical Frog".