Sm3+,Eu(3+)-codoped TiO2 nanoparticles were prepared by a facile sol-gel-solvothermal method. Sm3+ and Eu3+ were successfully incorporated into a TiO2 lattice and resulted in intense emission lines with resolved crystal-field splitting, in spite of a large mismatch in ionic radius between trivalent lanthanides (Ln3+) and Ti4+. The intense sensitized emissions of Sm3+ and Eu3+ ions by TiO2 host were obtained at room temperature. In this case, Sm3+ also acts as a bridge to transfer energy from TiO2 host to Eu3+ ions, which was not observed in Eu(3+)-doped TiO2 nanoparticles. In comparison with direct excitation of lanthanide ions, the luminescence lifetimes of 4G5/2 of Sm3+ and 5D0 of Eu3+ were observed to be significantly prolonged upon excitation above TiO2 band-gap. A sensitization mechanism to illustrate the energy transfer from TiO2 to Sm3+ and Eu3+ was proposed based on the optical behaviors of the codoped nanoparticles.