If by Complex Games you mean RPGs (which all the games Tiptup listed were) then yeah, the PS1 definitely had more of those. The N64 was not the console of choice for RPG connesuiers.

If you're just talking about games that are more than simple button mashers, or mindless action, I'd say the PS1 wins out there, but not by as wide a margin. The problem with the N64 is that even though it has several of the best games ever made, those happen to be about the only games worth playing on it. Outside of stuff by Nintendo and Rare, the N64 library is kind of dire.