The　detection　of　blood　glucose　plays　a　crucial　role　in　clinical　practice,　and　the　innovative　use　of　sweat　as　a　substitute　for　blood　has　brought　significant　practical　value　in　the　detection　of　blood　glucose.　However,　lactic　acid　(LA)　has　been　found　to　be　the　main　interfering　substance　on　the　detection　of　glucose　in　sweat.　In　this　study,　a　photoelectrochemical　sensing　system　was　constructed　by　using　NiO　nanosheets　as　photosensitive　materials　and　molybdenum-based　polyoxometalate　clusters　(Mo-POM)　as　masking　agents.　Mo-POM,　an　ideal　electroncapturing　agent,　effectively　promoted　the　spatial　separation　of　photo-generated　charge　carriers　in　NiO　nanosheets,　thereby　enhancing　the　oxidation　rate　of　glucose　on　the　valence　band　of　NiO　and　significantly　improving　the　detection　sensitivity.　Mo-POM　also　exhibited　the　characteristics　of　an　electron　sponge,　facilitating　fast　and　reversible　multi-electron　transfer　reactions　and　effectively　masking　certain　redox　substances,　especially　lactic　acid,　thus　greatly　enhancing　the　selectivity　of　the　glucose　sensor.　The　photoelectrochemical　(PEC)　sensor　constructed　using　Mo-POM　has　excellent　sensing　capability　with　high　sensitivity　to　detect　glucose　at　a　minimum　concentration　of　1　nM.　The　detection　limit　of　the　sensor　is　0.33　nM　(S/N　=　3).　This　sensor　can　be　reliably　applied　to　the　detection　of　glucose　in　sweat　and　the　accuracy　of　the　results　was　verified　by　gas　chromatography-mass　spectrometry.