The electrochemical oxidation of SO2 on polycrystalline gold electrodes has been studied by means of cyclic voltammetry and in situ vibrational techniques. On bare gold electrodes, SO2 is irreversibly oxidised on forward scans at similar to0.6 V/RHE, featuring a diffusion-limited peak. Oxidation is inhibited by the formation of chemisorbed oxygen. A SO2 anodic current rise occurs on the reverse scan in parallel with the reduction of the metal oxide layers. As shown by FT-IR, oxidation proceeds to yield a mixture of soluble S(VI) species as stable reaction products. From vibrational spectra and results from the irreversible adsorption method, it follows that no strongly adsorbed S-O-like residues are present onto the gold surface in the region 0.3-0.5 V/RHE. On sulphur-modified electrodes improved electrocatalysis is manifested by the shift of the diffusion-limited peak to lower potentials. The best performance is observed at a sulphur coverage of 0.5. At higher coverage, sulphur adlayers impart lower catalytic efficiency and eventually show strong poisoning properties. This behaviour is exhibited by sulphur adlayers generated either in situ by SO2 reduction or ex situ by sulphide adsorption/oxidation in acidic or alkaline media. (C) 2000 Elsevier Science Ltd. All rights reserved.