A new microporous TiO2-pillared layered titanate has been successfully prepared by hybridizing the exfoliated titanate with the anatase TiO2 nano-sol. According to the X-ray diffraction analysis and N2 adsorption-desorption isotherms, the TiO2-pillared layered titanate showed a pillar height of ~2 nm with a high surface area of ~460 m2/g and a pore size of ~0.95 nm, indicating that a microporous pillar structure is formed. Its photocatalytic activity was evaluated by measuring the photodegradation rate of 4-chlorophenol during irradiation of catalyst suspensions in an aqueous solution. An enhancement in activity of ca. 170% was obtained for TiO2-pillared layered titanate compared to that of the pristine compound such as layered cesium titanate.