Abstract:　Highly　selective　photocatalytic　conversion　of　biomass-derived　chemicals　into　value-added　chemicals　and　clean　hydrogen　energy　under　mild　conditions　by　simultaneously　utilizing　photogenerated　holes　and　electrons　is　in　line　with　the　theme　of　sustainable　development　of　green　chemistry.　Herein,　a　two-dimensional　(2D)　heterostructure　of　ternary　Ni2P–graphene–lepidocrocite　TiO2　(NPG–TiO2)　with　intimately　interfacial　contact　has　been　successfully　fabricated,　which　exhibits　significantly　elevated　photocatalytic　performance　toward　coevolution　of　benzaldehyde　(2.17 mmol/h/g)　and　hydrogen　(1.97 mmol/h/g)　from　biomass-derived　benzyl　alcohol　in　aqueous　solution　under　the　visible　light　irradiation.　Mechanistic　studies　reveal　that　in　this　ternary　heterostructure,　graphene　serves　as　an　electron　relay　mediator　to　facilitate　the　flow　of　electrons　from　TiO2　to　Ni2P　due　to　its　inherent　electrical　conductivity,　and　the　Ni2P　provides　the　active　sites　for　photocatalytic　proton　reduction　to　hydrogen.　It　is　anticipated　that　this　work　would　make　a　contribution　to　rational　design　of　2D　flat-structured　multi-component　photocatalysts　for　selective　conversion　of　biomass-derived　chemicals　coupled　with　hydrogen　evolution.　Graphic　abstract:　[Figure　not　available:　see　fulltext.].　©　2019,　Springer　Nature　B.V.