Catalytic conversion of structurally different epoxides to the corresponding 1,2-diacetoxy esters was carried out readily with phosphomolybdic acid alone or its supported on $SiO_2$. The reactions were carried out under solvolytic or solvent free conditions within 5-15 min at room temperature. The product 1,2-diacetates were obtained in high to excellent yields. Supporting of phosphomolybdic acid on $SiO_2$ showed the better catalytic activity than $Al_2O_3$. Conversion of optically pure R-(+)-styrene oxide to S-(+)-1,2-diacetoxy-1-phenylethane was carried with phosphomolybdic acid in high yield and stereospecificity.