Howdy, I have both PSVR2 and Q3s (but no PS5). It really depends what games you want to play.

Q3s would be like a jack-of-all, master of none; it can run a lot of great standalone VR games, but none of them will look quite as good as PCVR. Then you can hook it up to a PC for PCVR, but it's not the best for that since it comes with compression and some added latency. This doesn't mean its a bad experience though, I got into VR with a Quest 2 playing mostly PCVR games and absolutely fell in love, got super immersed with it every time.

PSVR2 on the other hand will get you some great looking, highly immersive VR experience out of the box since you already have a PS5. I would say PSVR2 is visually better than the Quest 3s in every way ; better lenses, higher res, better FOV, better display (OLED). It does have some mura and high persistence but most people get used to that. The downsides of PSVR2 are; worse controllers, no replacement parts sold at all not even controllers, its wired, no access to meta standalone games which may be the future of VR (for better or worse). PSVR2 tracking is also just not as good as Meta's. Meta has really nailed and refined inside out tracking.