Catalyst precursor was prepared with the Fe-Al hydrotalcite as the support, Ce-doped TiO2 as the active component. Then SO42-/CeO2-TiO2/HTLC photocatalyst was obtained by SO42- -modification with soak method. Catalysts were characterized by means of XRD, SEM-EDS and UV-Vis DRS. With methyl orange as model pollutant, the photocatalytic performance of the catalysts was determined. Experimental results showed that the absorption intensity for visible light of the CeO2-TiO2 particle was stronger than that of TiO2 particle; moreover there was a synergistic effect between SO42- and CeO2-TiO2/HTLC, thus the absorption intensity for visible light of SO42-/CeO2-TiO2/HTLC photocatalyst was enhanced further. The decolorization rate for methyl orange of modified SO42-/15%(CeO2-TiO2)/HTLC photocatalyst reached 93% after irradiation under simulated sunlight for 2 hours.