TiO2 pillared montmorillonite was synthesized by microwave irradiation, and the best synthesis condition was determined on the basis of a discussion on the influence of irradiation power and irradiation time. Samples with photodegradation methyl orange performance was studied in comparison with samples synthesized by the traditional method. When microwave irradiation power is 70%, TiO2 is well crystallized with anatase as the major form, which enhances the photocatalytic performance of the sample. The pillared structure exists well when the surface area is relatively large (237 m2/g), which also enhances the photocatalytic performance of the sample. In comparison with the sample synthesized by the traditional method, TiO2 pillared montmorillonite synthesized by microwave irradiation has well crystallized TiO2, with anatase being the major form, and there exists better photocatalytic performance of methyl orange under UV light.