Rare earth doped silica films were prepared by sol-gel method accompanied with the spin-coating process. It was found that the photoluminescence (PL) property of the thin films was dependent strongly on the doping amount of Eu3+. For thin films annealed at 700 ℃, the PL intensity increased constantly as elevating the doping amount up to 10% without any evident concentration quench, which indicated the good doping property of the SiOmatrix. In order to further improve the PL efficiency, co-doping of Tb3+ into SiO∶Eu3+ thin films were also investigated. It was found that the luminescence intensity was obviously enhanced by co-doping which could be explained in terms of the effective energy transfer from Tb3+ to Eu3+.