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I'm not sure what's the best I've ever heard, but there are some really good ones out there. If you've just completed a 5.1 setup, you can say goodbye to forced dynamic range compression forever. It makes quite a difference, I can tell you!
Inception sounds pretty danged awesome. Huge dynamic range, powerful bass response, and excellent surround usage. The score is important to the film and is allowed to achieve prominence when it needs to.
Some of the Pixar movies have quite impressive mixes. The Incredibles in particular stands out to me because its surround panning is some of the best I've encountered. I have only have standard 5.1, but I imagine that with the EX rear channel it would sound even better.
Out of all the Bond films, I think GoldenEye has the most satisfying mix on an artistic level. True, they did use a lot of sound effects from older recording libraries, so it can be a bit low-fi at times, and its LFE is kind of boomy and one-note, but I love the way it sounds anyway. It's just so well put together—the surrounds integrate very well, dynamics are impressive, and you've gotta love the way the bass just dominates and gets in your face in some places. I highly recommend watching a version that pre-dates the Ultimate Editions, because even though the remixed track cleans up some distortion, its bass response is so much lower than the original most of the time that it can't compare.
Casino Royale is very good also, although in a completely different sort of way. It sounds a lot more "modern" somehow, but is an example of a newer sound done right.
I just watched X-Men 2 yesterday, and found myself quite drawn in by that. Not much bass most of the time, but it didn't feel like it was missing anything, and the surround usage more than makes up for it, anyway. I really like the sounds they used for the various mutant powers, and the score is terrific.
Terminator 2 is another good one. The sound of Arnold's shotgun is the thing I remember most clearly, but this is just a well done mix in general.
I recall the most recent Narnia film, Voyage of the Dawn Treader, having quite a good mix also. It was surprising just how immersive it actually was, although I don't recall many specific details off the top of my head.
Editing to add: Can't believe I forget this, but Master and Commander has to be the most utterly realistic recording that's ever been made. All the little sounds are put together so well that you can really believe you're actually on the sailing ship with the characters, and that's something very few mixes are able to achieve. In addition, the cannon fire is so powerful it's almost as if you're really being shot at in the midst of all the chaos. A very large and powerful subwoofer is needed to truly represent all the super-deep bass present here.
By the way, I heard a rumour that the original version of Star Wars had some really great mono surround stuff going on . . . ;)
