HPW/MCM-41 catalyst was prepared by supporting phosphotungstic acid(HPW) on mesophases MCM-41 molecular sieves by immersion method.MCM-41 molecular sieves were synthesized by hydrothermal synthesis method with tetraethylorthosilicate (TEOS) as silica source and cetyltrimethylammonium bromide(CTAB) as surfactant.The catalysts were characterized by X-ray diffraction(XRD),FTIR,transmission electron microscopy(TEM).The original Keggin structure of HPW and mesophases structure of MCM-41 molecular sieves were maintained after supporting HPW on MCM-41molecular sieves.The HPW/MCM-41 is applied to synthesis reaction of ethyl acetate,and the catalytic performance is investigated.