Photocatalysis　has　become　an　increasingly　popular　method　to　treat　pharmaceuticals　and　personal　care　products　(PPCPs)　in　a　water　matrix　due　to　its　green　and　energy-saving　nature.　However,　the　development　of　highefficiency　catalysts　to　remove　such　refractory　organic　pollutants　still　faces　many　challenges.　Herein,　an　urchin-like　composite,　Bi/W18O49,　was　designed　and　prepared　via　solvothermal　process　followed　by　magnetron　sputtering　method.　The　photocatalytic　performance　of　Bi/W18O49　for　PPCPs　removal　proved　to　be　superior　under　red　light　(610　nm,　1.23E4　lm)　compared　with　pure　WO3　or　W18O49,　due　to　better　light　absorption　property　and　frequency　matching　between　the　stronger　plasmon　resonance　(dual-LSPR　effect)　and　incident　light　irradiation.　Thorough　experiments　were　conducted　to　identify　the　unique　properties　of　Bi/W18O49,　and　they　demonstrated　that　the　composite　state　contained　plenty　of　oxygen　vacancies　and　the　dual-LSPR　effect　was　vital　to　the　efficient　removal　for　pollutants,　as　the　effect　guarantees　OV　level,　hot　electron　transfer,　stable　light　response　ability　and　more　positive　potential.　The　photocatalytic　results　show　that　the　removal　efficiency　of　trimethoprim,　acetaminophen,　and　tetracycline　by　Bi/W18O49　could　reach　93　%,　87　%,　and　62　%,　respectively.　Combined　with　density　functional　theory　(DFT)　calculations　and　analysis,　trapping　tests,　and　LC-MS　measurement,　the　degradation　pathways　of　those　pollutants　were　described　in　detail　as　well.　Additionally,　different　influencing　factors　such　as　the　concentration　of　catalyst　and　pollutants,　pH　of　the　solution,　various　inorganic　and　organic　species　were　comprehensively　investigated,　and　the　reusability　and　stability　property　of　the　product　performed　well.　To　the　best　of　our　knowledge,　this　is　the　first　time　such　Bi/W18O49　composite　was　prepared　and　applied　in　treating　PPCPs,　representing　a　new　strategy　for　effective　wastewater　treatment　via　the　construction　of　LSPR　materials.