Abstract: It is reported the esterification reaction of acetic acid with alcohol on HZSM -5 zeolite. With a series of HNaZSM-5 zeolite catalysts, the effect of the degree of cation exchange on the activities and the selectivities of the catalysts were discussed. The effect of calcination temperature of HZSM-5 zeolite on the activity and the selectivity was investigated. The surface acidity of HZSM-5 zeolite was determined by JR-spectroscopic method. It Was found that the esterification reaction can take place both at the Bronsted acid sites and the Lewis acid sites, while ether was produced mainly at strong Bronsted acid sites. Since the activity of the catalyst was not reduced remarkably by 4-mcthylquinoline, the esterification must mainly occured on the internal surface of zeolite.