Abstract Efficiently assembling amino acids and peptides with bioactive molecules facilitates the modular and streamlined synthesis of a diverse library of peptide‐related compounds. Particularly notable is their application in pharmaceutical development, leveraging site‐selective late‐stage functionalization. Here, a visible light‐induced three‐component reaction involving arylthianthrenium salts, amino acid/peptide derivatives, and alkenes are introduced. This approach utilizes captodatively‐stabilized carbon radicals to enable radical‐radical C─C coupling, effectively constructing complex bioactive molecules. This method offers a promising alternative route for modular synthesis of peptide‐derived bio‐relevant compounds