A novel 18F labeling strategy was developed to directly construct aryl-SO2-18F from arenediazonium tosylates with a SO2 source and [18F]fluoride. This approach is compatible with a wide range of substrates and enabled the production of 18F-labeled drug-like derivatives through late-stage 18F fluorination, representing a significant advance in the radiosynthesis of 18F-labeled arenesulfonyl fluorides. A reactive 18F labeling synthon, bearing a maleimide-based prosthetic group, allowed for the generation of 18F-labeled temperature-sensitive biomolecules containing cysteine residues via maleimide-cysteine chemistry.