The catalytic effects of a triarylamine [(2,4-Br2C6H3)(3)N] (2) for the fluorodesulfurization of S-aryl thiobenzoates were investigated by cyclic voltammetry. It was found that the electron transfer from S-p-methoxyphenyl thiobenzoate to 2(+.) was fast while that from S-phenyl and S-p-chlorophenyl derivatives to 2(+.) was slow. The indirect macro-electrolysis of S-aryl thiobenzoates gave benzoyl fluoride in good yield at a less positive potential compared with direct electrolysis. A possible mechanism for triarylamine mediated fluorodesulfurization was proposed.