Heterogeneous　photocatalytic　degradation　of　antibiotic　involves　the　activation　of　antibiotic　molecules　and　the　photocatalytic　oxidation　process.　However,　the　simultaneous　improvement　of　these　processes　is　still　a　challenge.　Herein,　S-scheme　heterojunctions　consisted　of　Cu2O　nanocluster　with　defective　WO3　nanosheets　were　constructed　for　efficient　photocatalytic　degradation　of　levofloxacin　(LVX).　The　typical　CNS-5　composite　(5　wt%　Cu2O/WO3)　achieves　an　optimal　LVX　degradation　efficiency　of　97.9%　within　80　min.　The　spatial　charge　separation　and　enhancement　of　redox　capacity　were　realized　by　the　formation　of　S-scheme　heterojunction　between　Cu2O　and　WO3.　Moreover,　their　interfacial　interaction　would　lead　to　the　loss　of　lattice　oxygen　and　the　generation　of　W5+　sites.　It　is　witnessed　that　the　C–N　of　piperazine　ring　and　C[dbnd]O　of　carboxylic　acid　in　LVX　are　coordinated　with　W5+　sites　to　build　the　electronic　bridge　to　activate　LVX,　greatly　promoting　the　further　degradation.　This　work　highlights　the　important　role　of　selective　coordination　activation　cooperated　with　S-type　heterojunctions　for　the　photocatalytic　degradation　and　offers　a　new　view　to　understand　the　degradation　of　antibiotics　at　molecular　level.　©　2024　Elsevier　Ltd