Ternary　composites　of　reduced　graphene　oxide　(GR)-CdS-Pd　have　been　successfully　synthesized　via　solvothermal　and　photodeposition　methods　for　photocatalytic　selective　conversion　of　benzyl　alcohol　(BA)　coupled　with　hydrogen　(H2)　production,　which　exhibit　significantly　improved　photoactivity　and　selectivity　than　bare　CdS.　Mechanistic　studies　unveil　that　the　cooperative　effect　of　the　close　interface　contact　and　matched　energy　level　alignment　between　electrical　conducting　GR　nanosheets　(NSs)　and　CdS　nanoparticles　(NPs)　in　GR-CdS-Pd　composite　not　only　benefits　the　separation　and　transfer　of　photogenerated　carriers　but　also　improves　the　photocorrosion　resistance　of　CdS.　The　photodeposited　Pd　NPs　further　promote　the　photogenerated　charge　separation　and　accelerate　the　formation　of　intermediate　products　(α-hydroxybenzyl　radicals),　thereby　contributing　to　enhanced　conversion　of　BA.　This　work　would　facilitate　the　rational　design　of　GR　as　cocatalyst　to　construct　an　efficient　and　stable　CdS-based　composite　photocatalyst　for　cooperative　coupling　of　fine　chemical　synthesis　and　H2　evolution.　©　2023