Single oxygen (1O2) generated in peroxymonosulfate (PMS) activation parades great prospects in substituting common free radicals (∙OH/∙SO4−) for remediating wastewater. Unlike traditional modified approach, our study focused on optimizing partial atom orbital hybridization interaction with defects and altering charge transfer from catalysts to PMS, committed to pursue high selectivity of 1O2 (non-radical activation). Herein, CoxNi3-xS2-V nanoparticles are synthesized in situ on nickel foams (NF) through a hydrothermal/Joule heating method and applied to PMS activation as immobilized catalysts. The result indicates that the Co0.50Ni2.50S2-V sample can totally activate PMS to mineralize ciprofloxacin with highest kinetic constant (0.2236 min−1) and excellent resistance to environment factors. Assisted by quantitative tests, singlet oxygen (1O2) was verified as the dominant active species and the proportion of non-radical activation was increased to 86.91 %. Furthermore, theorical calculation revealed that this precise pathway regulation is attributed to the adsorption state adjustment and the reduction of Gibbs free energy for *O (transition state) and *1O2 production. Our research provides novel insights into selective regulation of 1O2 for efficient and sustainable wastewater remediation.