This study presents a novel electrophotocatalytic strategy for the hydrogenation of imines and reductive functionalization of aryl halides. The key innovation is the generation of a long-lived closed-shell thioxanthone-hydrogen anion species (3) under electrochemical conditions, which can be photochemically converted into a potent reductant. This species enables efficient hydrogenation of imines and reductive transformations of aryl halides without the need for chemical reductants. The system utilizes a combination of photochemistry and electrochemistry, leveraging the advantages of both to achieve high selectivity and efficiency. The closed-shell anion species 3 has a long excited-state lifetime, allowing it to effectively reduce substrates. The study demonstrates that the presence of TfOH regulates the redox potential of the active species, enabling the reaction to proceed at low potential and minimizing competitive hydrogen evolution. The developed method allows for the hydrogenation, borylation, stannylation, and (hetero)arylation of aryl halides, forming C–H, C–B, C–Sn, and C–C bonds. The mechanism involves the reduction of the precatalyst to form species 3, which is then photoexcited to generate a potent reducing agent. The study also explores the substrate scope, showing that a wide range of imines and aryl halides can be effectively functionalized. The results highlight the potential of this strategy for broad applications in organic synthesis, offering a sustainable and efficient alternative to traditional methods. The approach avoids the use of expensive transition metals and chemical reductants, making it a promising platform for future developments in catalytic chemistry.This study presents a novel electrophotocatalytic strategy for the hydrogenation of imines and reductive functionalization of aryl halides. The key innovation is the generation of a long-lived closed-shell thioxanthone-hydrogen anion species (3) under electrochemical conditions, which can be photochemically converted into a potent reductant. This species enables efficient hydrogenation of imines and reductive transformations of aryl halides without the need for chemical reductants. The system utilizes a combination of photochemistry and electrochemistry, leveraging the advantages of both to achieve high selectivity and efficiency. The closed-shell anion species 3 has a long excited-state lifetime, allowing it to effectively reduce substrates. The study demonstrates that the presence of TfOH regulates the redox potential of the active species, enabling the reaction to proceed at low potential and minimizing competitive hydrogen evolution. The developed method allows for the hydrogenation, borylation, stannylation, and (hetero)arylation of aryl halides, forming C–H, C–B, C–Sn, and C–C bonds. The mechanism involves the reduction of the precatalyst to form species 3, which is then photoexcited to generate a potent reducing agent. The study also explores the substrate scope, showing that a wide range of imines and aryl halides can be effectively functionalized. The results highlight the potential of this strategy for broad applications in organic synthesis, offering a sustainable and efficient alternative to traditional methods. The approach avoids the use of expensive transition metals and chemical reductants, making it a promising platform for future developments in catalytic chemistry.