Can't rank them.
Deus Ex
X-COM (seriously, both of these after all these years are still top 5)
Civ 4 (soon to be Civ 5)
UT2004
Warcraft 3 (I wish I could sub this with SC2, but in its current form SC2 is just horrible, mostly cause of B.net 2.0)
I really really wanted to put Diablo 2 in there, however I can't get it over Deus Ex. If you absolutely demand a brand new game list, put these in for DE and XCOM:
Potal
World of Goo