The photophysics surrounding the electron and hole trapping in TiO2 do not have a scientific consensus. Herein, we studied the steady-state photoluminescence and time-resolved spectroscopy time-resolved photoluminescence indicates that the electrons from bandgap excitation decay slower (similar to 30 ps) than in TiO2 (< 24 ps). We conclude this as a result of the band bending passivation effect on the surface electron traps. Meanwhile, electron trapping is proved as the dominant surface depopulation process because of the easy-fill characteristics of surface hole traps even under low excitation density, which also interprets the slow surface hole trapping (similar to 2 ns) in TiO2. Through plasmon-assisted electron injection, we distinguished the electron and hole behaviors at varied photon fluences and then obtained the intrinsic bulk trapping of electrons and holes in the similar to 50 and similar to 400 ps time range, respectively.