It　is　crucial　to　develop　highly　efficient　full-spectrum-responsive　S-scheme　heterojunctions　for　wastewater　purification.　Herein,　an　innovative　Zn3In2S6/WO3−x　heterojunction　was　synthesized,　featuring　full-spectrum　responsiveness.　It　achieved　100　%　inactivation　of　methicillin-resistant　Staphylococcus　aureus　(MRSA)　in　45　min　and　90.34　%　photocatalytic　degradation　of　tetracycline　(TC)　in　120　min.　Its　effectiveness　was　mainly　due　to　rapid　charge　separation　via　the　S-scheme　electron　transfer　pathway　and　near-infrared　light　absorption　from　the　Localized　Surface　Plasmon　Resonance　(LSPR)　effect　of　WO3−x.　Importantly,　it　showed　robust　photocatalytic　capacity　under　diverse　conditions.　Quenching　experiments　and　EPR　analysis　confirmed　that　·OH　and　·O2−　played　essential　roles　in　photocatalytic　degradation.　Intermediate　products　were　identified　using　LC-MS,　3D　EEMs,　and　TOC,　revealing　the　degradation　pathway.　Quantitative　structure–activity　relationship　(QSAR)　analysis　suggested　reduced　ecotoxicity　of　pollutants.　A　potential　mechanism　for　enhanced　sterilization　and　photocatalytic　degradation　was　proposed.　This　study　provides　a　theoretical　and　experimental　basis　for　designing　novel　heterojunctions　for　solar-assisted　water　purification.　©　2025　Elsevier　Ltd