I'm not going to be content till ALL of these games are included:
1994
System Shock
Heretic
Doom II
Marathon
Star Wars: Tie fighter
Warcraft: Orcs and Humans
(X-Com) UFO: Enemy Defence
Beneath the Steel Sky
Prince of Persia 2
Worms
Wing Commander III
CyClones
ShadowCaster CD
Alone in the Dark 2
Raptor
Quarantine
Earth Siege
The Fortress of Dr Radaki
Depth Dwellers
Operation Body Count
1995
Star Wars: Dark Forces
Marathon 2: Durandal (Win = 1996)
.Command & Conquer
Descent
Rise of the Triad
HeXen
X-Com: Terror of the Deep
MechWarrior 2: 31st Century
Super Street Fighter II Turbo
Crusader: No Remorse
Star Wars: Rebel Assault II
I have no Mouth, I must Scream
Cybermage: Darklight Awakening
Earthworm Jim
Dark Seed II
Wipeout
Mortal Kombat II
Sim City 2000 Special Edition
Witchaven
The Terminator: Future Shock
Wrath of Earth
Elder Scrolls Arena
Spear of Destiny 2 & 3
1996
Final Doom
Duke Nukem 3D
Eradicator
Abuse
Quake (WinQuake '97)
Descent II
.Command & Conquer: Red Alert
Tomb Raider
Alien Trilogy
Crusader: No Regret
Diablo
Warcraft 2: Tides of Darkness
Area 51
Necrodome
Broken Sword: Shadow Templars
Die Hard Trilogy
Earthworm Jim 2
Elder Scrolls 2: Daggerfall
Strife: The Quest for Sigil
Civilisation II
Shattered Steel
Alone in the Dark 3
ZPC (v. interesting)
Wing Commander IV
1997
Blood, One Unit Whole
Shadow Warrior
Hexen II
Quake 2
Fallout
Dungeon Keeper
Star Wars:Jedi Knight-Dark Forces2
Star Wars: X-Wing vs Tie Fighter
Postal
Turok: Dinosaur Hunter
Total Annihilation
Tomb Raider II
X-Men: Children of the Atom
X-Com Apocalypse
Blood Omen: Legacy of Kain
(PowerSlave) Exhumed
Chasm: The Rift
Virtua Squad 2 (Virtua Cop 2)
Grand Theft Auto
Resident Evil
Redneck Rampage
Broken Sword 2
MDK
Outlaws
1998
.Half Life
.Fallout 2
.Thief: The Dark Project
Commandos: Behind Enemy Lines
Heretic II
Grim Fandango
Curse of Monkey Island
Star Wars: Shadows of the Empire
Rainbow Six
Starcraft
Starsiege: Tribes
Tomb Raider III
Unreal
Worms 2
Blood 2
Heart of Darkness
Final Fantasy VII
Forsaken
Future Cop LAPD
Aliens Online
SiN
Shogo: Mobile Armor Division
Baldur's Gate
Die by the Sword
1999
System Shock 2
.C&C: Tiberian Sun
Unreal Tournament
Quake III Arena
Turok 2: Seeds of Evil
Rainbow Six: Rogue Spear
South Park
Star Wars: X-Wing Alliance
Dungeon Keeper 2
Rayman 2: The Great Escape
Legacy of Kain: Soul Reaver
Tomb Raider: The Last Revelation
X: Beyond The Frontier
MechWarrior 3
Indiana Jones: Infernal Machine
FreeSpace 2
Descent 3
Resident Evil 2 Platinum
Worms Armageddon
Homeworld
Outcast
Star Wars: Episode 1 Racer
Star Wars: Rogue Squadron
Planescape Torment
2000
.Thief 2: The Metal Age
.Deus Ex
,Soldier of Fortune
.Aliens vs Predator Gold
.Hitman: Codename 47
No One Lives Forever
Descent 3
Diablo II
.C&C: Red Alert 2
Resident Evil 3
Fur Fighters
Tomb Raider: Chronicles
Star Wars: Force Commander
Dino Crisis
Crimson Skies
Typing of the Dead
Quake 3: Team Arena
Counter-Strike
Shogun: Total War
Metal Gear Solid: Integral
Bauldur's Gate II
MDK 2
Evolva//American McGee's Alice
Codename: Eagle
That's my personal "top 24 By year" every year from 1994 to 2000. I don't see the point including 2001 and onwards as all those games support Windows XP which by extension includes the latest Op Sys windows 7 so no emulation needed. That's the main feature of GOG, the guarantee of full functionality with modern PCs.