Electrophotochemical CH Functionalization of Alkanes via Metal‐Catalyzed Hydrogen Atom Transfer

The direct and selective functionalization of unactivated C(sp 3 )H bonds under mild conditions represents a fundamental challenge in synthetic chemistry owing to their high bond dissociation energies and intrinsic nonpolarity. The integration of ligand‐to‐metal charge transfer (LMCT)‐enabled hydrogen atom transfer (HAT) with electrochemistry has emerged as a mild and sustainable strategy. This review provides a dedicated overview of recent advances in electrophotochemical C(sp 3 )H functionalization enabled by decatungstate, cerium‐based, and iron‐based catalytic systems, covering both net‐oxidative transformations coupled with cathodic hydrogen evolution and redox‐neutral processes through Fe/Ni‐based paired electrolysis. It details the mechanistic insights, highlights the unique advantages, and discusses current challenges and future directions for this promising approach to C(sp 3 )H bond valorization.