[en] The sluggish Ni(II)/Ni(III) redox cycle does not benefit perxymonosulfate (PMS) activation for recalcitrant pollutant degradation. To solve this problem, a heterogeneous catalyst, Cu_0.2Ni_0.8O/SBA-15 (CNS), was constructed to activate PMS for decomposing two sulfonamide antibiotics, sulfachlorpyridazine (SACP) and sulfapyridine (SAP). SACP and SAP were completely degraded over Cu_0.2Ni_0.8O/SBA-15/PMS (CNSP) after 90 min. O₂^.- was the dominant active species involved in the degradation of SACP and SAP. Structural analysis and elemental valence state observations indicated that Cu(Ⅰ) provided electrons through Cu–O–Ni bonds to realize the charge compensation for Ni(Ⅲ) in the CNSP system. Thus, the in situ Cu(I)/Cu(II) promoting the Ni(II)/Ni(III) cycle could accelerate the PMS activation. This work provides new insights into the electron transfer between transition metals and the charge compensation mechanism for PMS activation. The degradation mechanism was proposed based on the XPS results before and after the reaction, a radical quenching test, and an EPR test. Combined with the SACP and SAP degradation intermediates identified by LC-MS, we suggest that the choice of treatment process depends on the occurrence of a steric hindrance effect between the molecular structure of the degradation target and free radicals.