The persistence and wide dispersion of antibiotics have a severe impact on the ecological environment. Developing an effective method with universal applicability to remove pollutants is pretty necessary. Herein, a bimetallic oxides (Co3V2O8) heterogeneous material was successfully prepared and used to activate the persulfate (PS) for purification of tetracycline (TC) wastewater. By exploring the reaction conditions and influencing factors, the removal rate of 50 mg⋅L-1 TC reached 87.1% by Co3V2O8/PS system, and the reaction rate constant was up to 0.0271 min−1. As a highly efficient catalyst for the activation of PS, Co3V2O8/PS system produces radicals of SO4•−, •OH, •O2– and 1O2 in the reaction process due to the Co(II) and V(IV) exchange electrons with S2O82- and O2. Simultaneously, the internal electron exchange occurs between Co(II)/Co(III) and V(IV)/V(V), which stabilizes the content of Co(II) and V(IV). This work provides a novel activator for PS activation to degrade contaminants and contributes to a better understanding of the PS activation mechanism by transition compound.