We　have　designed　a　novel　semiconductor　core/layer　nanostructure　of　a　uniform　ZnO@TiO2　nanorod　array　modified　with　a　ZnIn0.25Cu0.02S1.395　solid-solution　on　the　surface　via　a　facile　hydrothermal　synthesis.　This　novel　nanostructure　combines　the　merits　of　all　components　and　meets　the　requirements　of　photovoltaic　system　application.　An　intimate　PN　heterojunction　is　formed　from　the　ZnO@TiO2　nanorod　and　polymetallic　sulphide　solid-solution,　which　is　remarkably　beneficial　for　the　effective　visible　light　absorption　and　rapid　charge　carrier　separation.　The　nanostructures　exhibit　higher　photocurrent　and　incident　photon　to　electron　conversion　efficiency　(IPCE)　under　no　bias　potential　versus　the　Ag/AgCl　electrode.　We　also　analyzed　the　interface　and　photoelectrochemical　characteristics　of　the　nanostructure　and　revealed　the　kinetic　process　of　the　electron　and　hole　transmission.　In　addition,　the　photoanode　test　shows　the　hydrogen　production　capability　of　the　nanostructures　from　solar　water　splitting.　These　results　verified　that　the　ZnO　and　TiO2　can　be　sensitized　by　the　polymetallic　sulfide　for　UV-Vis　light　driven　energy　conversion.　Importantly,　the　approach　we　used　to　design　the　photoanode　enables　the　development　of　micro-nano　electronic　devices　with　enhanced　performance.