The electronic structure of (Pb,La)(Zr,Ti)O3 (PLZT) thin film was studied by X-ray absorption spectroscopy and soft-X-ray emission spectroscopy (SXES). The Ti 3d and O 2p partial densities of states in the valence band region were observed in O 1s and Ti 2p SXES spectra. The energy position of the Ti 3d state overlapped with that of the O 2p state, indicating the occurrence of the hybridization effect between the Ti 3d and O 2p states. The hybridization effect of PLZT thin film is lower than that of Pb(Zr,Ti)O3 thin film. This finding indicates that the hybridization effect is closely related to the change in the bond length between Ti and O ions.