Electron　transfer　is　an　important　way　to　activate　persulfate.　Currently,　the　electrons　for　persulfate　activation　mainly　originate　from　organic　contaminants　or　the　catalyst　itself,　which　can　lead　to　selective　activation　of　persulfate　or　oxidation　of　the　catalyst,　respectively,　and　thus　become　a　bottleneck　restricting　its　application.　In　this　work,　Cu−doped　FeVO4　(Cu−FVO)　was　prepared,　and　the　results　showed　that　Cu　doping　can　significantly　improve　the　photocatalytic　activity　and　stability　of　FVO　for　peroxymonosulfate　(PMS)　activation.　The　optimized　Cu−FVO/PMS/light　system　exhibited　a　high　BPA　degradation　rate　that　is　4.3　times　higher　than　that　of　the　FVO/PMS/light.　This　system　manifested　a　broad　applicability　to　various　organic　contaminants　even　with　complex　matrix.　Photoelectrochemical　analysis　and　DFT　theoretical　calculations　revealed　that　Cu　doping　boosted　the　photogenerated　charge　separation　and　the　adsorption　of　PMS　on　FVO.　Furthermore,　Cu　doping　led　to　the　establishment　of　an　electron　transfer　channel　from　Cu−FVO　to　PMS,　through　which　photogenerated　electrons　achieved　an　efficient　PMS　activation.　Meanwhile,　holes　were　consumed　by　organic　contaminants　to　avoid　the　oxidation　of　catalyst.　These　collectively　enhanced　the　photocatalytic　activity　and　stability　of　Cu−FVO,　which　also　maintained　high　catalytic　activity　even　after　20　cycling　degradation　reactions.　©　2024　SIOC,　CAS,　Shanghai,　&　WILEY-VCH　GmbH.