A gold-catalyzed divergent dechlorinative radical borylation of gem-dichloroalkanes is reported, enabling the synthesis of structurally diverse alkyl boronic, α-chloroboronic, and gem-diboronic esters in moderate to good yields (up to 92%). The reaction utilizes dinuclear gold complexes and visible light irradiation, overcoming the redox potential limitations of alkyl chlorides through inner-sphere electron transfer. The method is robust and applicable to late-stage diversification of complex molecules. The process involves C-Cl bond relay activation in readily available gem-dichloroalkanes, enabling the formation of various borylated products, including gem-diboronic, α-choroboronic, and boronic esters. The reaction conditions were optimized using various photocatalysts, boron sources, and solvents, with the optimal conditions involving dinuclear gold complex (PC1), B₂cat₂ as the radical boron source, and N,N-diethylformamide (DEF) as the solvent. The reaction scope was extensive, including a variety of gem-dichloroalkanes with different functional groups, such as nitriles, esters, and furan. The method was also applied to the synthesis of complex molecules, demonstrating its utility in organic synthesis. The reaction mechanism involves the formation of a gold complex, which absorbs visible light to generate a triplet excited-state species, leading to inner-sphere single-electron transfer and the formation of chloroalkyl radicals. The reaction was further optimized using continuous-flow synthesis, enhancing the efficiency and yield of the reaction. The method provides a versatile platform for the synthesis of various borylated compounds, including α-chloro alkylboronic esters, which are useful building blocks in organic synthesis. The reaction was also applied to the synthesis of various natural products and pharmaceuticals, demonstrating its broad applicability. The study highlights the importance of gold-catalyzed reactions in the synthesis of complex molecules and the potential of visible light irradiation in enabling efficient and selective borylation reactions.A gold-catalyzed divergent dechlorinative radical borylation of gem-dichloroalkanes is reported, enabling the synthesis of structurally diverse alkyl boronic, α-chloroboronic, and gem-diboronic esters in moderate to good yields (up to 92%). The reaction utilizes dinuclear gold complexes and visible light irradiation, overcoming the redox potential limitations of alkyl chlorides through inner-sphere electron transfer. The method is robust and applicable to late-stage diversification of complex molecules. The process involves C-Cl bond relay activation in readily available gem-dichloroalkanes, enabling the formation of various borylated products, including gem-diboronic, α-choroboronic, and boronic esters. The reaction conditions were optimized using various photocatalysts, boron sources, and solvents, with the optimal conditions involving dinuclear gold complex (PC1), B₂cat₂ as the radical boron source, and N,N-diethylformamide (DEF) as the solvent. The reaction scope was extensive, including a variety of gem-dichloroalkanes with different functional groups, such as nitriles, esters, and furan. The method was also applied to the synthesis of complex molecules, demonstrating its utility in organic synthesis. The reaction mechanism involves the formation of a gold complex, which absorbs visible light to generate a triplet excited-state species, leading to inner-sphere single-electron transfer and the formation of chloroalkyl radicals. The reaction was further optimized using continuous-flow synthesis, enhancing the efficiency and yield of the reaction. The method provides a versatile platform for the synthesis of various borylated compounds, including α-chloro alkylboronic esters, which are useful building blocks in organic synthesis. The reaction was also applied to the synthesis of various natural products and pharmaceuticals, demonstrating its broad applicability. The study highlights the importance of gold-catalyzed reactions in the synthesis of complex molecules and the potential of visible light irradiation in enabling efficient and selective borylation reactions.