Merging hydrogen (H ) evolution with oxidative organic synthesis in a semiconductor-mediated photoredox reaction is extremely attractive because the clean H 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 H 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 H production and then focus on the fundamental principles of cooperative photoredox coupling of selective organic synthesis and H 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 H 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.