Oxidative dehydrogenation of n-butene to 1,3-butadiene over sulfated ZnFe2O4 catalyst was carried out in a continuous flow fixed-bed reactor. The effect of sulfation on the catalytic performance of ZnFe2O4 was investigated. Sulfated ZnFe2O4 catalyst showed a better catalytic performance than ZnFe2O4 catalyst in the oxidative dehydrogenation of n-butene. Acid-base property of sulfated ZnFe2O4 catalyst was measured by TPD experiment, with an aim of correlating the catalytic performance with the surface acid-base property of the catalyst. It was revealed that the catalytic performance of sulfated ZnFe2O4 catalyst was closely related to the surface weak-acid density of the catalyst. The enhanced acidity of sulfated ZnFe2O4 catalyst was responsible for its high catalytic performance in the oxidative dehydrogenation of n-butene. Thus, sulfation served as an efficient method for improving catalytic performance of ZnFe2O4 in the oxidative dehydrogenation of n-butene.