The　Schottky　barrier　created　at　the　interface　between　electron　sinks　and　semiconductors　can　effectively　optimize　electron　transfer　for　active　photocatalysis.　However,　heterogeneous　photocatalytic　organic　transformations　via　the　Mott　Schottky　effect　are　still　rare　and　their　role　in　the　specific　photocatalytic　system　remains　ambiguous.　Here,　a　versatile　photocatalytic　system　integrating　the　Schottky　junctions　into　the　TiO2　particles　(Degussa,　P25)　and　Pd　NP　based　films　has　been　developed.　They　were　readily　available　through　the　facile　encapsulation　of　P25　by　Pd-H4BINDI　films　using　an　alternating　layer-by-layer　(LBL)　approach　(H4BINDI:　N,N′-bis(5-isophthalate　acid)naphthalene-diimide).　After　a　H2　reduction　process　under　200　°C,　the　Pd　NPs　were　obtained,　denoted　as　P25@Pd-H4BINDI-200.　Interestingly,　the　resulting　P25@Pd-H4BINDI-200　photocatalyst　presented　an　exceptionally　high　activity　for　dehydrogenation　and　hydrogenolysis　of　benzyl　alcohol　under　visible　light　irradiation,　which　was　approximately　17　times　higher　than　that　of　the　parent　P25@Pd-H4BINDI　and　was　superior　to　any　other　analogous　systems　reported　to　date.　Specifically,　the　negative　charges　accumulated　on　the　Pd　NP　surface　reduce　the　benzyl　alcohol,　while　the　holes　left　on　the　valence　band　oxidize　the　benzyl　alcohol,　effectively　promoting　photocatalytic　cycles　with　enhanced　carrier　separation.　The　deeper　understanding　of　the　reaction　mechanisms　revealed　that　Pd　NPs　play　a　vital　mediating　role　in　storing　and　shuttling　photogenerated　electrons　via　the　Mott　Schottky　effect,　and　revealed　the　highly　enhanced　carrier　separation　by　direct　use　of　photoexcited　electrons　and　holes　for　photoredox　reactions.　This　work　holds　great　promise　for　designing　Mott-Schottky　catalysts　in　enabling　solar-driven　photoredox　reactions.　This　journal　is　©　The　Royal　Society　of　Chemistry.