Take Waugh-Type (NH4)6[MnMo9O32] •8H2O absorbed on diatomite and prepared supported solid catalyst. The properties of the catalyst were studied through the synthesis of benzyl acetate. The appropriate reaction conditions were obtained by orthogonal test: mole ratio of acetic acid to benzyl alcohol was 2.5:1.0, the catalyst dosage was 1.6g, the water carrying agent toluene dosage was 2.5ml, reaction time was 150min, esterification yield was 87.4%. The catalyst are high catalytic activity and non- polluting, and could be reused.