The electrocatalytic determination of SO2 is studied as a function of pH at a glassy carbon electrode modified with iron(II)tetrasulfophthalocyanine ([Fe(II)TSPc]4−). It was found in the literature that depending on pH, SO2·xH2O, HSO3− and/or SO32− are the main compounds in solution, that these compounds behave differently at the electrode surface, and that the condition of the electrode surface is stable over the entire pH-range. The use of SO2(g) or sodium sulfite as starting material did result in identical curves except in the pH range from 7.5–9.0. A possible explanation could be given by proposing that SO2·xH2O is very unstable in the presence of SO32−. In strongly acidic medium, SO2·xH2O is the main compound, which can be oxidized as well as reduced with exchange of two electrons. HSO3− is the main compound at pH = 4 and can also be oxidized and reduced with exchange of, respectively, two and four electrons. In alkaline solution sulfite is the main compound and can only be oxidized, also under exchange of two electrons. Detection limits are in the range of 4.0 ± 0.1 × 10−5 and 7.5 ± 0.1 × 10−5 mol L−1, dependent of pH and of the type of reaction (oxidation or reduction) used.