Developing　the　Co-based　catalysts　with　high　reactivity　for　the　sulfate　radical　(SO4−·)–based　advanced　oxidation　processes　(SR-AOPs)　has　been　attracting　numerous　attentions.　To　improve　the　peroxymonosulfate　(PMS)　activation　process,　a　novel　Co-based　catalyst　simultaneously　modified　by　bamboo　carbon　(BC)　and　vanadium　(V@CoO-BC)　was　fabricated　through　a　simple　solvothermal　method.　The　atenolol　(ATL)　degradation　experiments　in　V@CoO-BC/PMS　system　showed　that　the　obtained　V@CoO-BC　exhibited　much　higher　performance　on　PMS　activation　than　pure　CoO,　and　the　V@CoO-BC/PMS　system　could　fully　degrade　ATL　within　5 min　via　the　destruction　of　both　radicals　(SO4−·　and　O2−··)　and　non-radicals　(1O2).　The　quenching　experiments　and　electrochemical　tests　revealed　that　the　enhancing　mechanism　of　bamboo　carbon　and　V　modification　involved　four　aspects:　(i)　promoting　the　PMS　and　Co　ion　adsorption　on　the　surface　of　V@CoO-BC;　(ii)　enhancing　the　electron　transfer　efficiency　between　V@CoO-BC　and　PMS;　(iii)　activating　PMS　with　V3+　species;　(iv)　accelerating　the　circulation　of　Co2+　and　Co3+,　leading　to　the　enhanced　yield　of　reactive　oxygen　species　(ROS).　Furthermore,　the　V@CoO-BC/PMS　system　also　exhibited　satisfactory　stability　under　broad　pH　(3–9)　and　good　efficiency　in　the　presence　of　co-existing　components　(HCO3−,　NO3−,　Cl−,　and　HA)　in　water.　This　study　provides　new　insights　to　designing　high-performance,　environment-friendly　bimetal　catalysts　and　some　basis　for　the　remediation　of　antibiotic　contaminants　with　SR-AOPs.　©　The　Author(s),　under　exclusive　licence　to　Springer-Verlag　GmbH　Germany,　part　of　Springer　Nature　2024.