The game has a slower pace due to the fact that players miss a lot more passes if you just want to trade the ball around between players all at the 1st touch of the ball. You have to be alot more aware of the players' positions and distances to have a successful ball trade between them. The ball won't always go where you'd want it to be when doing long through passes, be it through ground or air. You have to do them with a certain stance and at a certain distance (and of course, with the right players) to get them as close as you'd wish to their destination.
Players are a lot more intelligent this time, be it defence or offense.
Defenders are much more aware of their opponents' positions in the field and are able to track them much more accurately, which means you won't need to babysit them as much as you did in PES4 in order to be able to intercept passes. They'll be able to do that for you a lot more, leaving you free to worry about other stuff when defending.
On offense they're smarter too, because they now enjoy shooting the ball with the foot in crosses or rebounds while the ball is still on air, making for some spectacular volleys and whatnot, and since the collision detection is so great in this game, you could have shots where the player doesn't quite hit the ball directly, and then the shot goes like hitting the ground and then fooling the goalkeeper while it rebounds off the ground and jumps over the helpless guy.
The referee is alot smarter this time. He'll call almost almost all tackles correctly, and now there's even smart stuff that didn't happen before, like having a player brutally fouled, but waving "play on" (playing advantage), and then when the play ends, he gets near the player who commited foul and gives him a yellow card. There's now other stuff, like when your player has a yellow card and commits another hard foul, the ref can reach directly for the red card without showing first the second yellow (he always showed the 2nd yellow in PES4).
During those little replays in offsides and shots at goal that don't go in, it's now up the player who's on offense to decide whether he wants to watch the replay or not, whereas any player in PES4 could take away the replay, making for some angry faces, when you'd want to see your dangerous shot one more time or weren't sure that the offside playcalling was correct. Of course, in online mode neither of you could take away the replay (but i didn't play online in PES5 yet, so i can't comment on that).
The only thing worse that i've noticed so far, is that in some very rare shots, if you use the Y button to make your keeper come after the ball, he can sometimes just stop there looking at whatever he's looking and the ball just rolls over to the back of the net. It's stupid and happened twice on the same day to me. Weird..... (didn't happen in PES4)
That's all for now, you can ask other stuff if you want.