A simple and effective electrochemical biosensor with good analytical properties such as fast response, long-time stability, and good detection range has been developed for the determination of sulfite. The modification of SPCEs with TTF and SOX clearly improves the sensitivity for the analysis of this compound, exhibiting a linear response to sulfite in a wide concentration range. Its capability of detection, estimated for a probability of false positive (α) and negative (β) of 0.05, slightly improves from 9.9 to 6 μM when working at 60 °C. This easy modification procedure of SPCEs led to the amperometric determination of sulfite at +200 mV vs a screen-printed Ag/AgCl electrode. Since interferences are avoided at this low potential, the developed biosensor can be successfully applied to the determination of sulfite in white and red wines.