Saw this today and quite enjoyed it. It had (as most posters have recognized) a very 1960s feel to it: the fashions, the music, the slightly freewheeling spirit, the Cold War, the split screens, the European locations used as if we'd never seen them before and for no apparent reason - like, why was one scene set at a motor racing track? No reason, just looks good.
There was lots of little sharp one-liners and the interplay between all the lead characters was excellent. The action was well edited and framed and didn't seem to over power the actors or the story, which is a common fault of most modern actioners. I liked the quick explanatory flashbacks that made clear some of what we'd witnessed earlier in the movie. I thought Cavill particularly was very good. I was very impressed with the sequence where he decides whether or not to commit to a rescue, sipping wine and chewing lunch as he does so. This was an excellent scene which tells you much about his character.
My only real sticky point was the 'origin' nature of the film. I agree with Kaplan (below); there really was no need for them to show how UNCLE was formed. I always assumed UNCLE had been around years before either Solo or Kuriyakin came on the scene. The way they managed it here seemed to suggest its less of a United Nations espionage department and more a gang of rogue agents meshed together to form a secret club.
None the less a thoroughly enjoyable movie. Probably better than MI:RN for me, but only because I always preferred UNCLE to MI.