H3PW12O40Ti(OH)4 hydrogel was prepared by the sol-gel method, and then H3PW12O40TiO2/bentonite was prepared through the intercalation of H3PW12O40Ti(OH)4 into interlayer space. The characterization of XRD, SEM and EDS showed that H3PW12O40TiO2 species were successfully immobilized on bentonite, and the layer strucure of bentonite was changed. The discrete anatase TiO2 existed on the bentonite. H3PW12O40TiO2/bentonite was a composite material with the different particle size and th loose structure. The photocatalytic degradation of methyl orange showed that the photocatalytic activity of catalyst had been better by doping H3PW12O40, and the H3PW12O40/TiO2/bentonite had a wide applicable range of pH value. Moreover, H3PW12O40TiO2/bentonite had a good catalytic stability. Based on the results of characterization analysis and catalytic performance, the schematic procedure for the action mechanism of H3PW12O40TiO2/Bentonite in photocatalysis was presented.