Persulfate-based　advanced　oxidation　technologies　(PS-AOPs)　show　great　potential　in　treating　emerging　pollutants　because　of　their　multiple　reaction　pathways　induced　by　a　variety　of　reactive　species.　However,　the　modulation　of　the　reactive　species　in　PS-AOPs　and　the　specificity　of　reactive　species　for　contaminants　have　still　not　received　adequate　attention.　In　this　work,　the　feasibility　of　pH　on　modulating　reactive　species　in　PS-AOPs　mediated　by　single-atom　Co　catalyst　(CoSA)　and　the　relationship　between　each　species　and　contaminant　were　deeply　discussed.　In　the　CoSA/PMS　system,　Co(IV)　was　the　predominantly　active　species　in　acidic　conditions,　and　1O2　was　the　predominantly　active　species　in　neutral　and　alkaline　conditions.　Specific　degradation　relationships　with　various　pollutants　were　explored　based　on　different　major　active　species　regulated　under　different　pH　conditions.　Density　Functional　Theory　(DFT)　and　experimental　results　demonstrated　that　organic　pollutants　with　high　EHOMO　(Energy　of　the　Highest　Occupied　Molecular　Orbital),　low　VIP　(Vertical　Ionization　Potential)　and　ΔE　(Energy　Gap)　were　susceptible　to　oxidative　degradation.　Sulfonamide　compounds,　phenol　compounds　and　tetracycline　compounds　tended　to　be　attacked　by　1O2.　And　the　carbamazepine　compounds　and　quinolone　compounds　tended　to　be　attacked　by　Co(IV).　This　study　will　provide　new　perspectives　on　reactive　species　regulation　and　specific　degradation　of　pollutants,　and　offer　innovative　ideas　for　rapid　remediation　of　emerging　pollutants　in　aquatic　environments.　©　2025　Elsevier　Inc.