Herein, we demonstrated a visible light mediated tandem oxidation‒organo catalyzed C‒S bond functionalization protocol for the cleavage of aromatic C‒S bond. The investigation encompassed the functionalization of C‒S bonds within sulfones, sulfoxides, and aliphatic sulfide derivatives. However, the process of functionalizing the C‒S bond in aromatic sulfides remains uncertain. The presented protocol demonstrates the C‒S bond functionalization on benzo[b]benzo[4,5]thieno[2,3-d]thiophene derivative and amines including primary and secondary amines as well. A radical mediated mechanism was proposed for the tandem oxidation‒organocatalyzed C‒S bond functionalization protocol.