keeveek: I've heard Gods and Kings for Civ 5 is quite good.
Also, if you play Paradox games, expansions for Crusader Kings 2 are nice and not that expensive. Unless you doesn't want to play as muslim or restore byzantine empire
Paradox in general normally has good expansions for the games that they publish. Also note that most of the expansions also come with fixes for the core game as well and thus often make for a very worth while investment.
Zolgar: Diablo: Hellfire
Diablo 2: Lord of Destruction
Titan Quest: (whatever it was called)
Warhammer 40K Dawn of War: Dark Crusade
Bleh i have issues with calling a Stand Alone release (eg Dark Crusade) as an expansion ;)
Also you totally left Starcraft 2 Brood Wars off the list ;)
As for other expansions that really added to the core game:
Baldur's Gate 2 The Throne of Baal
Total Anihillation had two great expansions which added some new campaigns and some big new toys (buzzsaw super gun!)
Neverwinter Nights has had 3 really powerful expansions - although I would note that with their addition the skills list became somewhat overloaded with options.
Warcraft 3 The Frozen Throne - new units, new maps and a great expansion of the core games campaign!
(and if we count stand alone releases then Homeworld Cataclysm deserves to be on the list ;))