This study describes a light-driven method for generating α-bimetalloid radicals by selectively activating multifunctional C1 units using a Lewis base and light. The process involves the photoactivation of amphiphilic C1 units to form α-bimetalloid radicals, which can then react with various SOMOphiles to produce organic scaffolds with multiple synthetic handles. The method relies on the formation of a photoactive charge transfer complex involving 2,6-lutidine, which stabilizes iodine radicals and facilitates the activation of the C–I bond. Theoretical and mechanistic studies highlight the role of the boron p-orbital in weakening the C–I bond and the importance of 2,6-lutidine in stabilizing the resulting radicals. The approach enables the efficient synthesis of functionalized 3D frameworks that can be further modified using available technologies for C–B and C–Si bond activation. The method is simple, efficient, and complementary to existing organometallic and transition metal technologies. The study demonstrates the potential of this strategy for exploring chemical space through the controlled activation of multifunctional systems, with applications in the synthesis of complex molecules and the development of new therapeutic agents. The results show that the method can be used to access stereodivergent Z-isomers and enable chemoselective derivatization of products, highlighting its utility in drug discovery and synthetic chemistry.This study describes a light-driven method for generating α-bimetalloid radicals by selectively activating multifunctional C1 units using a Lewis base and light. The process involves the photoactivation of amphiphilic C1 units to form α-bimetalloid radicals, which can then react with various SOMOphiles to produce organic scaffolds with multiple synthetic handles. The method relies on the formation of a photoactive charge transfer complex involving 2,6-lutidine, which stabilizes iodine radicals and facilitates the activation of the C–I bond. Theoretical and mechanistic studies highlight the role of the boron p-orbital in weakening the C–I bond and the importance of 2,6-lutidine in stabilizing the resulting radicals. The approach enables the efficient synthesis of functionalized 3D frameworks that can be further modified using available technologies for C–B and C–Si bond activation. The method is simple, efficient, and complementary to existing organometallic and transition metal technologies. The study demonstrates the potential of this strategy for exploring chemical space through the controlled activation of multifunctional systems, with applications in the synthesis of complex molecules and the development of new therapeutic agents. The results show that the method can be used to access stereodivergent Z-isomers and enable chemoselective derivatization of products, highlighting its utility in drug discovery and synthetic chemistry.