In　the　past,　the　synthesis　of　polyoxometalate　(POM)-templated　silver　nanoclusters　typically　relied　on　the　use　of　organic　salts　of　POMs　as　starting　templates,　thereby　limiting　the　solvent　selectivity　in　the　synthesis.　The　utilization　of　pure-inorganic　POMs　as　starting　templates　in　developing　novel　POM-templated　silver　nanoclusters　has　been　neglected.　Herein,　we　have　used　pure-inorganic　polyoxoniobates　as　a　starting　template　to　synthesize　a　new　silver　nanocluster　H4[Nb6O19@Ag40(iPrS)28S4]　(Ag40)　(iPrS　=　isopropylthiolate).　Single-crystal　X-ray　diffraction　analysis　showed　that　the　silver　nanocluster　exhibits　a　remarkable　core-shell　structure　featuring　a　Lindqvist-type　[Nb6O19]8−　polyanion　as　a　template,　surrounded　by　40-nucleated　silver　ions　as　the　metal　shell　and　capped　by　iPrS−　ligands.　Interestingly,　the　silver　nanocluster　exhibits　significant　fluorescence　properties　at　low　temperatures,　demonstrating　temperature-dependent　fluorescence,　making　it　a　potential　candidate　for　temperature　sensing.　This　work　provides　a　new　strategy　for　new　POM-templated　silver　nanoclusters　by　using　pure-inorganic　POMs　as　starting　templates.　It　also　offers　new　insights　into　the　anionic　template　method　for　synthesizing　silver　nanoclusters.　©　2025　The　Royal　Society　of　Chemistry.