Low-cost and efficient catalysts are decisive for the broadened implementation of advanced oxidation processes (AOPs) in wastewater remediation. Based on the modified hypothesis by inducing a nonradical pathway, we designed the N-doped Co₃O₄ (N-Co₃O₄) for peroxydisulfate (PDS) activation by facile post-treatment of Co₃O₄ with N precursor at low temperature. The N-Co₃O₄/PDS system exhibited excellent degradation efficiency (98.7 %) in 1 h for the removal of typical organic pollutant (acid organic 7), enhanced by 41.4 % compared to Co₃O₄/PDS. Remarkably, distinguish from sluggish degradation by Co₃O₄, N-Co₃O₄ achieved an enhanced kinetic process with the degradation efficiency of 97.7 % in 5 min, making it outstanding to save time and economic costs. We discovered the activation mechanism by N-Co₃O₄ covered the nonradical pathways of singlet oxygen (¹O₂) and electron transfer, overcoming the sole radical pathway of Co₃O₄. The emerging oxygen vacancies on N-Co₃O₄ boosted the generation of active ¹O₂ with ^•O₂⁻ intermediates, and benefited the electron transfer process with lower resistance. N doping introduced Co-N basic sites facilitated the PDS adsorption, improving the electron transfer capability. This study proposes a facile protocol to convert transition metal oxide to functional catalyst and demonstrates the immense potential to create nonradical dominated degradation.