The transformations of physicochemical properties on manganese oxides during peroxymonosulfate (PMS) activation are vital factors to be concerned. In this work, Mn3O4nanospheres homogeneously loaded on nickel foam are prepared, and the catalytic performance for PMS activation is evaluated by degrading a target pollutant, Acid Orange 7, in aqueous solution. The factors including catalyst loading, nickel foam substrate, and degradation conditions have been investigated. Additionally, the transformations of crystal structure, surface chemistry, and morphology on the catalyst have been explored. The results show that sufficient catalyst loading and the support of nickel foam play significant roles in the catalytic reactivity. A phase transition from spinel Mn3O4to layered birnessite, accompanied by a morphological change from nanospheres to laminae, is clarified during the PMS activation. The electrochemical analysis reveals that more favorable electronic transfer and ionic diffusion occur after the phase transition so as to enhance catalytic performance. The generated SO4•−and •OH radicals through redox reactions of Mn are demonstrated to account for the pollutant degradation. This work will provide new understandings of PMS activation by manganese oxides with high catalytic activity and reusability.