The　integration　of　photoelectrochemical　(PEC)　technology　with　persulfate-based　advanced　oxidation　processes　has　emerged　as　a　promising　approach　for　efficient　pollutant　removal　in　environmental　remediation.　Herein,　we　developed　a　novel　PEC　system　combining　a　Co3O4/BiVO4　(CO/BVO)　photoanode　with　a　CoFe2O4/carbon　paper　(CFO/CP)　cathode　for　activating　peroxymonosulfate　(PMS)　toward　bisphenol　A　(BPA)　removal.　The　enhanced　photogenerated　charge　separation　in　CO/BVO　and　the　PMS　activation　by　CFO/CP　in　the　PEC　system　enabled　complete　BPA　degradation　within　60　minutes　under　optimized　conditions　(1.0　V　bias,　1.0　mM　PMS).　The　influence　of　PMS　concentration,　applied　bias,　pH,　and　coexisting　anions　on　BPA　degradation　was　thoroughly　investigated.　Radical　scavenging　experiments　combined　with　electron　paramagnetic　resonance　analysis　identified　•SO4-,　•OH,　and　photogenerated　holes　as　dominant　reactive　species.　The　system　also　exhibited　good　stability　over　five　consecutive　cycles,　with　minimal　metal　ion　leaching.　This　work　demonstrates　the　potential　of　an　efficient　PEC　system　integrated　with　sulfate　radical-based　AOPs,　offering　an　innovative　approach　for　organic　pollutant　remediation　in　wastewater　treatment.　©　2025　Elsevier　Ltd