The　sluggish　electron　migration　rate　and　pronounced　electron-hole　recombination,　pose　significant　obstacles　to　achieving　high　photocatalytic　efficiency.　The　utilization　of　multiple　catalysts　for　the　construction　of　heterojunctions　can　effectively　enhance　charge　separation.　A　series　of　Keggin-type　hollow　dodecahedral　polyoxometalates　were　prepared　via　hydrothermal　synthesis,　and　their　molecular　orbitals　were　modified　through　the　addition　of　metal　elements.　The　incorporation　of　metal　elements　modulated　the　electronic　structure　of　polyoxometalates,　effectively　enhancing　the　electron　aggregation　capability　of　polyoxometalates.　Single-component　catalysts　often　face　serious　hole-electron　recombination.　In　order　to　solve　this　problem,　the　scheme　of　constructing　heterojunction　is　proposed　to　improve　the　electron　transport　efficiency.　By　immobilizing　ZnCdS　nanoparticles　onto　the　polyoxometalate　surface,　the　heterojunction　architecture　was　engineered　to　significantly　enhance　the　interfacial　charge　transfer　capability.　Density　Functional　Theory　(DFT)　calculations　and　the　experimental　results　indicate　that　the　modulation　of　metallic　components　renders　the　polyoxometalate　a　more　favorable　energy-level　orbital.　The　catalytic　mechanism　of　ZnCdS　and　KMoP　S-scheme　heterojunction　was　also　verified.　The　formation　of　S-scheme　heterojunctions　further　improves　the　electron　transfer　efficiency　compared　to　other　traditional　heterojunctions,　achieving　efficient　utilization　of　photo　generated　electrons　and　holes.　Additionally,　the　S-scheme　heterojunction　shifts　the　catalystʼs　d-band　center　closer　to　the　Fermi　level,　thereby　improving　electrical　conductivity.　This　article　provides　a　new　approach　for　energy　level　regulation　of　polyoxometalates　and　the　design　of　S-scheme　heterojunctions.　©　2025