I've honestly no idea since i'm old-school and most of my games are not linked to steam and the like, so i don't have an accurate measure.
But i'll list a few of the ones that i think should be over 100 hours:
Sim city 3000
Silver
Dungeon Keeper 1&2
Daggerfall, Morrowind, Oblivion, (NOT skyrim yet actually, been doing other things)
Fallout 3
Age of Empires 1,2
Empire Earth 1
Settlers 3
FF 3,7,9,10
Homeworld 1, 2, Cataclysm
Lords of Magic
Lords of the Realm 1,2
System shock 2
Deus Ex (and Human Revolution)
Gears of War 1,2,3 (Single player only, with more time for multiplayer but that doesn't count)
X3 Terran Conflict
Freelancer (easily over 200-300 hours, i've completed 7 playthroughs)
Freespace 1 (Collected all medals and full rank xD)
Tachyon The Fringe
Neverwinter Nights 1
Dungeon Siege 1
GTA 1
Vampire: The Masquerade
Assassins Creed 1
Garrysmod (technically multiplayer but i've spent over 100 hours building on singeplayer)
Gothic 1,2,3,4 (I love this series more than Elder Scrolls.)
Risen (Aka, Gothic 1 Mk2)
Sword of the stars 1
Space Empires 4
Pax Imperia (probably logged about 500+ hours on this game...)
There's probably a lot more... but i can't think without my game collection infront of me.