For those who aren't aware of the history of PC gaming, the very first ever PC game (believe it or not) was in 1962, called "Spacewar!" on a PDP-1 computer, back when computers and such technologies were unheard of yet during those times and when no one owned a computer until the early 1980s.
Anyways, I have a touch pick between the 1990s and 2000s, since the 1990s gave us Doom, Diablo, Wolfenstein 3D, Fallout, Quake, System Shock, Civilization and Half-Life 1. The 2000s gave us Battlefield, Left 4 Dead, Max Payne, Deus Ex, World of Warcraft, Portal and League of Legends.
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I think it was probably the 1990s going into the 2000s. Now, I don't mean that PC gaming is worse since then, but with the release of the Playstation in 1994, and the XBOX in 2001, consoles started chipping away at the dominance of PC gaming. When I was kid in the 80s and 90s, we had computer game / software stores (like Software ETC). Consoles had maybe a little corner. By the 2000s, if you walked into a Gamestop, you would find a shelf or rack for PC games. Now, with Steam and other online game platforms, it's hard to find any PC games in stores.0