Building　an　effective　heterogeneous　Fenton　catalyst　over　a　broad　pH　range　without　the　requirement　for　external　energy　input　is　still　challenging.　Herein,　a　vanadium-cobalt　bimetallic　catalyst　(Co-V-8)　are　employed　to　extended　a　pH　range　of　3–9　by　activating　H2O2　as　a　Fenton-like　catalyst.　The　Co-based　Co-V-8　catalysts　demonstrate　high　diclofenac　sodium　deterioration　efficiency　(98.2%)　under　both　acidic　and　alkaline　environments,　and　the　kinetic　reaction　rate　within　15　min　could　reach　0.288　min−1.　Crucially,　density　functional　theory　(DFT)　calculations　imply　that　the　Co-V-8　owned　a　narrower　band　gap　and　a　higher　Fermi　level,　which　beneficial　for　quickening　the　electron　transfer　process.　Results　showed　that　the　catalyst　modified　by　V　could　introduce　abundant　oxygen　vacancies,　promote　the　decomposition　of　H2O2　via　V3+　and　V4+,　and　enhance　the　conversion　of　Co3+　and　Co2+,　accelerating　the　formation　of　·OH,　·OOH,　·O−2　and　electron　transfer　process.　Additionally,　Co-V-8　promoted　the　utilization　rate　of　H2O2　exceeding　90%　and　exhibited　exceptional　catalytic　ability　in　cleaning　actual　pharmaceutical　wastewater.　This　research　offers　a　sustainable　separable　and　purification　technology　for　wastewater　remediation.　©　2025　Elsevier　Ltd