Using cesium nitrate and strontium nitrate as doping metal ions source, Cs-doped TiO2 and Sr-doped TiO2 photocatalysts were successfully synthesized through the hydrolysis of tetrabutyl titanate by an acid-catalyzed sol-gel method. The photocatalytic activities of these catalysts prepared at 600 °C for 2 h were evaluated by the degradation of methyl orange in aqueous solution under solar light irradiation, and the as-prepared samples with higher photocatalytic efficiency were characterized by means of X-ray diffraction (XRD) and UV-Vis absorption spectroscopy. The XRD patterns indicate that the crystal structure still remains as anatase phase for the doped samples, and the average crystal size of TiO2, 0.1 at% Cs-doped TiO2 and 0.3 at% Sr-doped TiO2 is 21.3, 13.1 and 10.8 nm, respectively. The band gap absorption shows red shift to the visible region for the doped samples from the UV-Vis spectrogram. The results show that the photocatalytic activity of TiO2 nanoparticles doped with Cs+ and Sr2+ exhibits a significant improvement and their degradation efficiencies are more than 30% in comparison with those of TiO2 under the same condition, and the optimal doping concentration is determined to be 0.1 at% and 0.3 at% for Cs+ and Sr2+, respectively.