Not buying a lot of PS5 launch titles, I've already finished Demon's Souls on PS3 and I still have other From game's to finish before I would go back to it. My first installs on PS5 will be:-
Miles Morales
Witcher 3 - yup, never played it, my first experience is going to be the PS5 patched version.
Ghost of Tsushima - waited for next gen before trying it
Last of Us 2 - only about 1/3 through the game.
Bloodborne - 2/3 through this on PS4.
No Man's Sky
Rocket League
COD Warzone
In consideration - Yakuza, Assassins Creed Valhala, Dirt 5, Borderlands 3, Days Gone.