Abstract: Three kinds of new type solid strong acid catalysts S₂O₈^2-/ZrO₂-Al₂O₃-M₂O₃(M=Cr,Ce,La) were prepared. Their crystal structure, surface area, acid strength and sulfur content were determined by means of XRD, BET, flow Hammett indicator method and chemical analysis. Their catalytic activities in esterification reaction of acetic acid with n-butanol were studied. The results showed that ZrO₂ in the catalysts mainly in tetragonal phase and few in monoclinic phase. The tetragonal phase of ZrO₂ and S₂O₈^2- are the key factors that guarantee the catalytic activity. Incorporation of appropriate amounts of metallic oxides(Cr₂O₃,Ce₂O₃,La₂O₃) into the catalyst favors the stabilization of sulfur species and surface area, which increase the activity sites on the catalyst. The experimental results showed that three catalysts S₂O₈^2-/ZrO₂-Al₂O₃(2%)-M₂O₃(1%)(M=Cr,Ce,La) had higher catalytic activity in mentioned esterification, with the conversion of acetic acid reached 96.8%, 95.7% and 96.1%, respectively. The preparation condition of the catalysts showed great influence on the catalytic activity.