OK here's my updated list:
Top priority: Mechwarrior 2, 3, and 4 with all expansions (possibly #1 as well)
High priority: Project IGI: I'm Going In
Tom Clancy's Splinter Cell: Pandora Tomorrow
Heavy Gear 2
Space Hulk 1 & 2
Medium priority: Prey (2006)
Oni
Alien vs Predator 2
Laser Squad
Low priority: Future Cop: L.A.P.D.
Take no Prisoners
On a side note, I would also very much like GOG to offer games that are, or will be, available on other platforms: Command & Conquer collection, HALO collection, Heretic and Hexen series, Max Payne series, WH40K: Space Marine, Rise of Nations, maybe newer Deus Ex games like Human Revolution and Mankind Divided (I don't know if they are good or would appeal to a fan of the original game).
Also: I have not included No One Lives Forever 1 & 2 in my list, because I have played them in the past and I have no particular urge to revisit them now, so technically speaking they are not among the games that
I wish most that GOG would bring to their store. If the title of this thread was "What games you think most should be on GOG", they'll go straight at the top of the list.
*** EDIT ***
toxicTom: Generally it would be cool to have more emulated classics, esp. from Amiga, but there the license situation (Kickstart ROMs) is a mess.
I am a bit undecided on this issue, and even more about console or even arcade games on GOG (if it's feasible at all, that is), given the site's strong focus on PC gaming, but as a past Commodore user, I think I would be happy if GOG gave me the possibilty to revisit at least some oldies (for example, for Space Hulk and Laser Squad I would actually prefer the Amiga versions, for nostalgic reasons of course), maybe even some C64 games.
And obviously I am talking about making things legally; if you don't care about such technicalities, then finding what you need on the Internet is super-easy.