The very first mission in Rogue Leader is the famous Death Star assault, right down to the station-exploding shot.
In "Imperial Academy Heist", you can hijack a TIE Fighter. At night, you just shoot the pilot and then capture his ship, but in the daytime, you disable the fighter while it's flying and force the pilot to hand the ship over. If you then follow the line of training TIE Fighters, you can slip through the campus unnoticed until you get to the shuttle.
There are two alternate reality levels where you play as Darth Freakin' Vader; in a ship with cluster missiles, no less.
Battle For Naboo
Several people have wondered how Anakin was able to fly into the Trade Federation Command Ship's hanger when the ship is allegedly heavily shielded. You learn in the final level it's because you took out the shields for him.
In one level you hijack an AT-AT and blow the ever-lasting shit out of a lot of expensive-looking Imperial stuff.