Developing　the　transition　metal　catalysts　with　high　reactivity　for　the　sulfate　radical　(SO4　-center　dot)　based　advanced　oxidation　processes　(SR-AOPs)　has　been　attracting　numerous　attentions.　To　improve　the　peroxymonosulfate　(PMS)　activation　process　mediated　by　Co-based　catalysts,　a　vanadium-cobalt　bimetallic　catalyst　(V@CoO)　was　fabricated　by　modification　vanadium　through　a　simple　solvothermal　method.　The　pollutants　degradation　experiments　showed　that　the　obtained　V@CoO　exhibited　much　higher　performance　on　PMS　activation　(5.55-8.33　times　larger　of　apparent　rate　constants)　than　pure　CoO,　and　the　V@CoO/PMS　system　could　quickly　degrade　various　organic　contaminants　within　5　min　under　the　attack　of　both　radicals　(SO4　-center　dot　and　O2-center　dot)　and　non-radicals　(1O2).　The　density　functional　theory　(DFT)　calculations　and　electrochemical　tests　revealed　that　the　enhancing　mechanism　of　V　modification　involved　four　aspects:　(i)　promoting　the　PMS　adsorption　on　the　surface　of　V@CoO;　(ii)　enhancing　the　electron　transfer　efficiency　between　V@CoO　and　PMS;　(iii)　activating　PMS　with　V3+　and　V4+　species;　(iv)　accelerating　the　circulation　of　Co2+　and　Co3+,　leading　to　the　promotion　on　the　production　of　reactive　oxygen　species　(ROS).　Furthermore,　the　V@CoO/PMS　system　also　exhibited　satisfactory　stability　in　a　broad　pH　range　and　good　efficiency　in　the　presence　of　co-existing　components　(HCO3-,　NO3-,　PO43-　,　Cl-　and　HA)　in　water.　This　study　will　provide　new　insights　to　designing　high-performance,　environment-friendly　bimetal　catalysts　and　some　basis　for　the　remediation　of　organic　contaminants　with　SR-AOPs.