This research investigates the electron transfer to arene sulfonyl fluorides and succinimides and their potential use as precursors for surface modification. It is part of a continuous study to understand electron transfer to sulfur-containing organic compounds. The electrochemical study was performed using cyclic voltammetry and electrolysis. The results obtained were rationalized with gas-phase computational calculations. A change in the electron transfer mechanism was observed with the change in substituents and the leaving group. The change in the mechanism was found to be dependent on the nature of the starting material, the location of the lowest unoccupied molecular orbital (LUMO), the position of the substituents, the oxidation potential of the leaving group, and phenomenon such as the S---O nonbonding interaction. In addition, arene sulfonyl compounds were found to be sulfur depositors on gold surface when used as precursors for gold surface modification.