ABSTRACT The efficient coupling of hydrogen production with the valorization of alcohol feedstocks presents a compelling strategy for sustainable energy and chemical synthesis. This review addresses the fundamental scientific challenge of selectively steering alcohol conversion beyond simple dehydrogenation toward value‐creating C–C coupling pathways, while simultaneously producing green hydrogen. We focus on the synergistic catalytic systems that enable this dual‐output transformation, emphasizing how the integration of oxidative upgrading and reductive H 2 evolution within a single cycle can achieve near‐ideal atom economy and closed‐loop carbon utilization. By systematically comparing photocatalytic, electrocatalytic, and photoelectrocatalytic platforms, we elucidate their distinct mechanisms in activating C–H bonds and managing key carbon‐centered intermediates (e.g., *CH 2 OH) under mild conditions. Central to the discussion are catalyst design principles that decouple proton‐ and electron‐transfer steps, regulate interfacial charge dynamics, and stabilize active sites for selective C–C coupling—thereby overcoming the classic activity‐selectivity trade‐off. Through a critical assessment of recent advances, performance bottlenecks, and scalability constraints, this review not only synthesizes the state‐of‐the‐art but also provides a forward‐looking perspective on transforming alcohols into versatile vectors for distributed hydrogen generation and circular chemical production. By bridging molecular‐level mechanistic insights with system‐level design considerations, this work aims to establish a foundational framework and guide future research toward high‐performance, integrated catalytic processes.
Ren et al. (Thu,) studied this question.