The catalytic behavior of self-made phosphomolybdic acid for esterification reaction under microwave irradiation was studied,and effects of catalyst amount,microwave power and irradiation time were investigated.Under the optimal conditions,i.e.,phosphomolybdic acid amount of 0.05 g,microwave power of 640 W and irradiation time of 40 min,n-butyl acetate yield could be achieved to 94.5%.