Wipeout is what caught my eyes and why I wanted to buy a PS1. But I couldn't afford one at launch.

I bought the PS1 initially to play TombRaider 2, amazing game!

The game that made the biggest first impression was Metal Gear Solid. The intro, seeing his breath in the cold, foot steps in the snow, it was revolutionary.

I was a N64 kid so most of the PS1 games I played, I didn't play until the PS2 or much later at which point the graphics weren't good anymore. We did rent a PS1 once and played the first Resident Evil game and it was almost as big a wow moment as Mario 64 was. Where Mario 64 wowed running around in a big beautiful 3D environment, RE wowed by it's story elements, shooting mechanics, and graphics/environment.

Final Fantasy 7 was the reason I bought the console and started paying attention to gaming again. I still remember when I saw the commercial for the first time, it blew me away. My friend was talking to me and I completely shut them out until the commercial was over. I had an SNES before that but playing games on it rarely felt immersive or meaningful--until I found Final Fantasy 6 in a used game store that my friend dragged me into. I'd played Final Fantasy (1) on the NES and didn't even know that there were more of them. FF6 instantly became my favorite game by a mile but I couldn't find anything else like it and kind of dropped out of gaming as a hobby. At least, until that FF7 commercial hit me like a bomb.

Honorable mentions to Gran Turismo, Suikoden, and Soul Blade, all of which were absolutely awesome experiences that still live in my memory.

Pandemonium, Gran Turismo, F1 96, RE, FF7.

Wipeout 2097 was the first game I ever played on my PS1 and it blew my mind! I felt like the coolest kid ever with the sense of speed the game had, the techno music, and the ability to have weapons.

Its probably Resident Evil.... or Final Fantasy 7.

RE was scary as f*** when I was a kid, playing it other kids on a big tv screen.
We would close the curtains in the room, so it was dark... and then play and some of those jump scares... man.

Meanwhile FF7 was just alround good time.

FF7, FFTactics and Resident Evil 2. All exceptional games.

Resident Evil... by far. Blew my freakin' mind.

Really, nobody?

Well, it will be me then: Ridge Racer, a release title iirc (I did not own a PS1, but a 64 and later a PC). Fresh out of the arcades, it was super impressive to see something akin to Daytona in a home console. Pretty cool stuff and Namco's System 22 was amazing for its time.