This Concept outlines cutting‐edge progress in catalytic and enantioselective radical reactions facilitated by redox‐active chiral Lewis acids upon visible light excitation. These catalytic systems exploit the high reactivity of radical species to enable efficient stereocontrolled radical recombination. We delve into the design, underlying mechanisms, and practical applications of these catalysts, aiming for precise stereocontrolled bond formation. The synergistic blend of chirality and reactivity has brought a new level of precision to enantioselective radical additions, reshaping the approach to asymmetric synthesis. This Concept focuses on the recent progress and effective application of redox‐active chiral Lewis acids, including Rh, Ir, Ga and Ni, in catalyzing enantioselective radical reactions, which offers a comprehensive perspective on modern methods and projecting future directions in enantioselective radical chemistry.