This　work　demonstrated　that　75　fold-enhanced　photocatalytic　hydrogen　production　over　SrTiO3/TiO2　heterostructures　by　Au　plasmon-enhanced　electron-phonon　decoupling　to　generate　more　amounts　of　energetic　electrons　for　solar　water　splitting.　Such　Au　modified　SrTiO3/TiO2　heterostructures　were　synthesized　by　a　facile　hydrothermal　post-photoreduction　method,　consequently　the　hydrogen　evolution　rate　is　467.3　μmol　g−1　h−1,　which　is　187　and　75　folds　enhancement　compared　with　TiO2　and　SrTiO3/TiO2　samples,　respectively.　Based　on　systematic　investigations,　it　is　proposed　that　the　internal　electric　field　(IEF)　between　the　interfaces　of　SrTiO3/TiO2　and　the　enhanced　near-field　amplitudes　of　localized　surface　plasmon　(LSP)　inhibit　the　recombination　of　photogenerated　electrons　and　holes　in　the　bulk　and　accelerate　the　interfacial　transfer　of　charge　carriers.　Simultaneously,　electron　spin　resonance　(ESR)　showed　the　change　of　Ti3+　species　in　SrTiO3/TiO2　microspheres,　mirroring　the　energetic　electron　transfer　process　from　Au　NPs　to　SrTiO3/TiO2　microspheres.　©　2019　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim