Reactive species, holes, and electrons in photoexcited nanocrystalline TiO2 films were studied by transient absorption spectroscopy in the wavelength range from 400 to 2500 nm. The electron spectrum was obtained through a hole-scavenging reaction under steady-state light irradiation. The spectrum can be analyzed by a superposition of the free-electron and trapped-electron spectra. By subtracting the electron spectrum from the transient absorption spectrum, the spectrum of trapped holes was obtained. As a result, three reactive speciestrapped holes and free and trapped electrons-were identified in the transient absorption spectrum. The reactivity of these species was evaluated through transient absorption spectroscopy in the presence of hole- and electron-scavenger molecules. The spectra indicate that trapped holes and electrons are localized at the surface of the particles and free electrons are distributed in the bulk.