Two-dimensional　catalytic　membranes　achieve　efficient　water　purification　technology　by　leveraging　their　unique　confined　structure　to　enhance　reaction　efficiency　between　reactive　species　and　pollutants.　However,　the　influence　of　ordered　interlayer　structure　in　2D　confined　membranes　on　pollutant　removal　remains　unclear.　In　this　study,　a　series　of　2D　membranes　with　varying　interlayer　ordering　degrees　were　fabricated　by　vacuum-filtrating　GO@Cox　nanosheets　containing　different　crystalline　layers　of　GO.　Catalytic　experiments　revealed　that　membranes　with　higher　interlayer　ordering　achieved　nearly　100　%　tetracycline　(TC)　removal　across　diverse　environments　under　an　ultralow　peroxymonosulfate　(PMS)　dosage　(0.025　mM).　Electron　paramagnetic　resonance　(EPR)　analysis　demonstrated　that　the　ordered　interlayer　structures　significantly　promoted　the　conversion　of　PMS　to　long-lived　singlet　oxygen　(1O2),　thereby　improving　oxidant　utilization　efficiency.　Through　density　functional　theory　and　molecular　dynamics　simulations,　we　identified　that　ordered　interlayer　structures　primarily　enhance　PMS　activation　efficiency　by　strengthening　electron　transfer　between　GO@Cox　and　PMS.　Simultaneously,　the　ordered　interlayer　structures　elevate　the　transmembrane　potential　energy　barrier　for　pollutants　to　intensify　interactions　between　reactive　species　and　contaminants,　ultimately　boosting　pollutant　removal.　This　work　systematically　elucidates　the　critical　role　of　interlayer　structural　ordering　in　governing　catalytic　water　treatment　performance　of　2D　membranes,　providing　new　insights　for　designing　high-performance　nanomembrane　materials.　©　2025