Herein, the synthesis of sulfur-modified CuCo2O4 (S-CuCo2O4) nanoparticles as a heterogeneous catalyst for peroxymonosulfate (PMS) activation was reported. The S-CuCo2O4 maintained the spinel structure and exhibited rich oxygen vacancies. Also, the presence of S atoms enlarged the specific surface area and created strong Lewis acid sites that both enhanced the adsorption ability toward PMS and CIP. Compared to the corresponding S-doped single oxides and CuCo2O4, the S-CuCo2O4 with the designed molar ratio of S and metal ions to be 10%, i.e., CCS-10, significantly improved the catalytic activity, indicating the synergism between Cu-O-Co bonds, the oxygen vacancies, and the Lewis acid sites. Under the optimal conditions of 0.1g.L-1 CCS-10 dosage, 0.2g.L-1 PMS, and natural pH, the CCS-10/PMS system could remove approximately 87% of CIP and 70% of TOC within 20min at a four-time higher rate than that of the pristine catalyst. This system showed the highest performance in the pH range from weak acidic to weak basic (pH 5.5 - pH 8.5). CCS10/PMS also displayed considerable efficiency in degrading various pollutants belonging to different categories (methylene blue (MB), carbamazepine (CBZ), bisphenol A (BPA), and sulfamethoxazole (SMX)). SO4•–, •OH, O2•–, and 1O2 active species were found to be responsible for CIP elimination. Finally, the PMS residual concentration was recorded to be 0.01g.L-1 after the reaction. Overall, this study could contribute a possible strategy to enhance the heterogeneous catalysts for the removal of organic pollutants.