Efficient　aromatic　alcohol　oxidation　with　simultaneous　H2　evolution　under　aqueous　conditions　is　achieved　in　a　polyoxometalate　(POM)-incorporated　ZnIn2S4　dual-functional　photocatalytic　system.　The　synergy　between　HPM　and　ZIS　contributes　to　the　formation　of　a　Z-type　heterojunction　structure　and　thus　enhances　redox　capacity.　Moreover,　the　sub-nanometer　size　of　POM　clusters　endows　molecular-level　interfacial　contact,　which　acts　as　an　＇electron　bridge＇　ensuring　faster　interfacial　charge　transfer　kinetics.　Therefore,　an　impressive　nearly　100%　yield　of　benzaldehyde　and　10.6　mmol·g−1·h−1　H2-evolution　rate　are　observed　for　POM/ZIS　nanocomposites　even　under　an　anaerobic　atmosphere　with　water　as　the　solvent.　This　is　the　first　application　of　POM-based　materials　in　the　anaerobic　oxidation　of　benzyl　alcohol　with　concomitant　H2　production.　This　study　expands　the　possibilities　for　designing　multifunctional　POM-based　photocatalysts　for　economic　and　ecological　photoredox　applications.　©　2022　Elsevier　B.V.