HT Games
No, NCAA Football 10 on the PSP does not support online multiplayer. The handheld version was built around single-player experiences like Dynasty Mode, Season Mode, and mini-games, along with local ad-hoc multiplayer for face-to-face matches between two PSP owners. It lacks the network infrastructure required for online matchmaking or ranked play.
Even if you track down a working copy today, the official servers have been shut down for years, and the game client doesn’t support modern third-party tunneling tools like XLink Kai—those were mostly used for PS2 and PS3 titles.