Merging　hydrogen　(H2)　evolution　with　oxidative　organic　synthesis　in　a　semiconductor-mediated　photoredox　reaction　is　extremely　attractive　because　the　clean　H2　fuel　and　high-value　chemicals　can　be　coproduced　under　mild　conditions　using　light　as　the　sole　energy　input.　Following　this　dual-functional　photocatalytic　strategy,　a　dreamlike　reaction　pathway　for　constructing　C-C/C-X　(X　=　C,　N,　O,　S)　bonds　from　abundant　and　readily　available　X-H　bond-containing　compounds　with　concomitant　release　of　H2　can　be　readily　fulfilled　without　the　need　of　external　chemical　reagents,　thus　offering　a　green　and　fascinating　organic　synthetic　strategy.　In　this　review,　we　begin　by　presenting　a　concise　overview　on　the　general　background　of　traditional　photocatalytic　H2　production　and　then　focus　on　the　fundamental　principles　of　cooperative　photoredox　coupling　of　selective　organic　synthesis　and　H2　production　by　simultaneous　utilization　of　photoexcited　electrons　and　holes　over　semiconductor-based　catalysts　to　meet　the　economic　and　sustainability　goal.　Thereafter,　we　put　dedicated　emphasis　on　recent　key　progress　of　cooperative　photoredox　coupling　of　H2　production　and　various　selective　organic　transformations,　including　selective　alcohol　oxidation,　selective　methane　conversion,　amines　oxidative　coupling,　oxidative　cross-coupling,　cyclic　alkanes　dehydrogenation,　reforming　of　lignocellulosic　biomass,　and　so　on.　Finally,　the　remaining　challenges　and　future　perspectives　in　this　flourishing　area　have　been　critically　discussed.　It　is　anticipated　that　this　review　will　provide　enlightening　guidance　on　the　rational　design　of　such　dual-functional　photoredox　reaction　system,　thereby　stimulating　the　development　of　economical　and　environmentally　benign　solar　fuel　generation　and　organic　synthesis　of　value-added　fine　chemicals.　©　2021　American　Chemical　Society.