Sulfoximines are synthetically important scaffolds and serve important roles in drug discovery. Currently, there is no solution to decarboxylative sulfoximination of benzoic acids; although thoroughly investigated, limited substrate scope and harsh reaction conditions still hold back traditional thermal aromatic decarboxylative functionalization. Herein, we realize the first decarboxylative sulfoximination of benzoic acids via photo-induced ligand to copper charge transfer (copper-LMCT)-enabled decarboxylative carbometalation. The transformation proceeds under mild reaction conditions, has a broad substrate scope, and can be applied to late-stage functionalization of complex small molecules.