The mesoporous silica pillared clay (SPC) incorporated with Keggin-type H(3)PW(12)O(40) (HPW) heteropoly acid was prepared by introducing HPW into clay interlayer template in an acidic suspension using sol-gel method. The materials are readily separable mesoporous materials with high specific surface areas. The results indicate that the surfactants play a decisive role in the introduction of HPW molecule and the pore formation. Moreover, the surface area and pore size of the materials can be controlled by the molecular length and functional groups of the surfactants. The formation mechanism of the materials was also proposed. The synthesized materials exhibited good catalytic performance in oxidative desulfurization of dibenzothiophene-containing model oil. Under the best conditions, the sulfur removal can reach up to near 100%. The excellent catalytic performance for oxidative desulfurization opens up new opportunities for applications of the synthesized materials in catalysis. (C) 2011 Elsevier B.V. All rights reserved.