The paper describes a novel method for the photoactivation of ambiphilic C1 units to generate α-bimetalloid radicals using only a Lewis base and light. This approach enables the rapid synthesis of organic scaffolds containing multiple synthetic handles (boron, silicon, and germanium) for subsequent orthogonal activation. The study highlights the crucial role of 2,6-lutidine in forming a photoactive charge transfer complex and stabilizing iodine radicals, as well as the influence of the boron p-orbital in weakening the C–I bond. The methodology is demonstrated through the construction of versatile frameworks and the exploration of chemical space, showcasing its potential for efficient access to functionalized 3D frameworks. The mild, catalyst-free protocol can be paired with energy transfer catalysis to achieve stereodivergent access to Z-isomers containing two functional handles.The paper describes a novel method for the photoactivation of ambiphilic C1 units to generate α-bimetalloid radicals using only a Lewis base and light. This approach enables the rapid synthesis of organic scaffolds containing multiple synthetic handles (boron, silicon, and germanium) for subsequent orthogonal activation. The study highlights the crucial role of 2,6-lutidine in forming a photoactive charge transfer complex and stabilizing iodine radicals, as well as the influence of the boron p-orbital in weakening the C–I bond. The methodology is demonstrated through the construction of versatile frameworks and the exploration of chemical space, showcasing its potential for efficient access to functionalized 3D frameworks. The mild, catalyst-free protocol can be paired with energy transfer catalysis to achieve stereodivergent access to Z-isomers containing two functional handles.