Recent Progress on Photoelectrochemical Organic Upgrading: A Review from Direct and Indirect Charge Transfer Pathway

Abstract Photoelectrochemical (PEC) organic upgrading at the anode, coupled with hydrogen evolution at the cathode, presents a promising strategy for enhancing solar energy utilization while simultaneously generating value‐added chemicals. Due to the complex and competitive nature of bond activation during organic oxidation, precise control over the number and direction of photo‐induced charge transfers at the photoanode/liquid interface is essential for achieving high production rates, selectivity, and substrate conversion. In this review, recent advances in PEC organic transformations, including dehydrogenation, oxygenation, and C─H functionalization, are summarized, with a focus on two distinct oxidative pathways: direct charge transfer and indirect oxidation mediated by reactive species. The interfacial charge transfer processes and associated reaction mechanisms are further discussed, along with key strategies for system optimization, such as surface engineering, optical modulation, vacancy control, and morphological tuning. Finally, current challenges and future perspectives in photoelectrode design, mechanistic understanding, product separation, reaction coupling, scale‐up, and techno–economic evaluation for the practical production of solar‐driven chemicals are highlighted