In this study, a highly efficient CuO/α-MnO2 bimetallic catalyst was synthesized by hydrothermal and calcination methods and employed as a peroxydisulfate (PDS) activator for the degradation of thiocyanate (SCN−) in aqueous phase. The effect of calcination temperature on the catalytic performance of CuO/α-MnO2 and the mechanism of the CM350/PDS system were studied. Under optimal conditions, almost 100 % of SCN− (100 mg/L) was degraded within 90 min. XRD, XPS, Raman, and H2-TPR analyses revealed that the catalytic performance was enhanced in the CM350 catalyst due to the formation of M-O-Cu+-like structures (M = Mn3+, Mn4+, Cu2+) through the combination of α-MnO2 with CuO. The structures exhibit excellent redox ability and facilitate electron transfer between Cu and Mn elements, thereby improving the activation effect of PDS. Besides, the Cu1.5Mn1.5O4 generated from the high calcination temperature was not conducive to the SCN− degradation reaction. Moreover, the mechanism study indicated that SO4·-, ·OH, and the electron transfer pathway mainly accounted for the SCN− degradation. This study provides some guidance for the synthesis of PDS activation materials and the treatment of industrial wastewater by an advanced oxidation process.