The Fifth Element - Bruce Willis, Milla Jovovich, Chris Rock - This flick is so rich in color, it can only be viewed properly on DVD.  SurroundSound adds a nifty effect too!

Independence Day - Will Smith, Bill Pullman, Jeff Goldblum - Has special edition version that has more scenes and develops the characters more than the theatrical release.  Also has alternate ending (actually the original ending) and many other extras.

Top Gun - Tom Cruise, Anthony Edwards, Kelly McGillis - Just plain better than the tradition VHS version.

Twister - Bill Paxton, Helen Hunt - Both visuals and sound are spectacular when run with component video and SurroundSound.

The Matrix - You won't believe the special effects you get on your own TV!  The bigger your screen, the better this one looks.

Mission: Impossible 2 - Tom Cruise - The only way to do the special effects justice.  The motorcycle chase scene is awesome!

Armageddon - Bruce Willis, Ben Affleck, Liv Tyler - Lots of extras on the DVD and the special effects are awesome!

Eagles: hell freezes over - This is the only music format DVD I've tried, but it is fantastic!