Radiocesium　remediation　is　of　great　significance　for　the　sustainable　development　of　nuclear　energy　and　ecological　protection.　It　is　very　challenging　for　the　effective　recovery　of　137Cs　from　aqueous　solutions　due　to　its　strong　radioactivity,　solubility　and　mobility.　Herein,　the　efficient　recovery　of　Cs+　ions　has　been　achieved　by　three　layered　vanadyl　oxalatophosphates,　namely　(NH4)2[(VO)2(HPO4)2C2O4]center　dot　5　H2O　(NVPC),　Na2[(VO)2(HPO4)2C2O4]center　dot　2　H2O　(SVPC),　and　K2.5[(VO)2(HPO4)1.5(PO4)0.5(C2O4)]center　dot　4.5　H2O　(KVPC).　NVPC　exhibits　the　ultra-fast　kinetics　(within　5　min)　and　high　adsorption　capacity　for　Cs+　(qmCs　=　471.58　mg/g).　It　also　holds　broad　pH　durability　and　excellent　radiation　stability.　Impressively,　the　entry　of　Cs+　can　be　directly　visualized　by　the　single-crystal　structural　analysis,　and　thus　the　underlying　mechanism　of　Cs+　capture　by　NVPC　from　aqueous　solutions　has　been　illuminated　at　the　molecular　level.　This　is　a　pioneering　work　in　the　removal　of　radioactive　ions　by　metal　oxalatophosphate　materials　which　highlights　the　great　potential　of　metal　oxalatophosphates　for　radionuclide　remediation.