Simultaneous　generation　of　H2　fuel　and　value-added　chemicals　has　attracted　increasing　attention　since　the　photogenerated　electrons　and　holes　can　be　both　employed　to　convert　solar　light　into　chemical　energy.　Herein,　for　realizing　UV-visible-NIR　light　driven　dehydrogenation　of　benzyl　alcohol　(BA)　into　benzaldehydes　(BAD)　and　H2,　a　novel　localized　surface　plasmon　resonance　(LSPR)　enhanced　S-scheme　heterojunction　was　designed　by　combining　noble-metal-free　plasmon　MoO3–x　as　oxidation　semiconductor　and　Zn0.1Cd0.9S　as　reduction　semiconductor.　The　photoredox　system　of　Zn0.1Cd0.9S/MoO3–x　displayed　an　unconventional　reaction　model,　in　which　the　BA　served　as　both　electron　donor　and　acceptor.　The　S-scheme　charge　transfer　mechanism　induced　by　the　formed　internal　electric　field　enhanced　the　redox　ability　of　charge　carriers　thermodynamically　and　boosted　charge　separation　kinetically.　Moreover,　due　to　the　LSPR　effect　of　MoO3−x　nanosheets,　Zn0.1Cd0.9S/MoO3−x　photocatalysts　exhibited　strong　absorption　in　the　region　of　full　solar　spectrum.　Therefore,　the　Zn0.1Cd0.9S/MoO3−x　composite　generated　H2　and　BAD　simultaneously　via　selective　oxidation　of　BA　with　high　production　(34.38　and　33.83　mmol·g−1　for　H2　and　BAD,　respectively)　upon　full　solar　illumination.　Even　under　NIR　light　irradiation,　the　H2　production　rate　could　up　to　94.5　mmol·g−1·h−1.　In　addition,　the　Zn0.1Cd0.9S/MoO3–x　composite　displayed　effective　photocatalytic　H2　evolution　rate　up　to　149.2　mmol·g−1·h−1　from　water,　which　was　approximate　6　times　that　of　pure　Zn0.1Cd0.9S.　This　work　provides　a　reference　for　rational　design　of　plasmonic　S-scheme　heterojunction　photocatalysts　for　coproduction　of　high-value　chemicals　and　solar　fuel　production.　©　2022　Dalian　Institute　of　Chemical　Physics,　the　Chinese　Academy　of　Sciences