In the present paper, the samples of nanomaterials TiO2—SiO2∶Eu3+ with different proportion of Ti/Si were prepared with the sol-gel method, and influence of the proportion of Ti/Si on the luminescence properties of samples have was studied. The structure of the samples was examined by FTIR, indicating that the compound TiO2 and SiO2 reacted, forming the new chemical bond of Ti—O—Si. The TEM of samples show that TiO2—SiO2∶Eu3+ are sphericity nanoparticles with monodispersion and uniform size of 35 nm. The samples were still anatase phase after annealing at 900 ℃, which was studied by XRD and SAED, suggesting that the bond of Ti—O—Si was conducive to the stability of anatase phase. There will be isoelectronic trap as Si4+ enters the TiO2 lattice replacing some of the Ti4+ position, and this structure is conducive to transfering energy and improving the transition of Eu3+ (7F0→5D2), which were found by excitation and emission spectra.