TiO2 pillared rectorite (TPLR) had been synthesized by sol-gel method, and was characterized by XRD, TEM, BET, UV-vis DRS and FTIR. The effects of calcination temperature on the microstructure and the photocatalytic activity of the as prepared catalyst were investigated. The photocatalytic activity of the catalyst was evaluated by decomposition of Acid Red B (ARB) aqueous solution. XRD patterns revealed that TiO2 is incorporated into the interlayer of the rectorite. TEM demonstrated that TiO2 particles are present in the rectorite. The BET analysis indicated that the surface area of the sample calcined at 300°C (TPLR-300) was larger than those of other samples. The TPLR samples had high adsorption capacity and good photocatalytic efficiency in decomposition of ARB in water. FTIR spectra of the original and the recovered samples indicated that the catalyst had not chemically changed during the photocatalytic reaction.