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A novel spectrofluorimetric method for the determination of sulfite using rhodamine B hydrazide as fluorogenic reagent in the presence of polyoxyethylene sorbitan monooleate (Tween 80) surfactant micelles is described. The method is based on the mixture of sulfite with rhodamine B hydrazide, a colorless, non-fluorescent substance in Tween 80 surfactant micelles which gives rhodamine B-like fluorescence emission. The fluorescence intensity increase is linearly related to the concentration of sulfite in the range 5–800 ng ml −1 with a detection limit of 1.4 ng ml −1 (3 σ ). The optimal conditions for the detection of sulfite are evaluated and the possible detection mechanism is also discussed. The method has been successfully applied to the determination of total sulfite in wines and compares well with the standard iodimetric method.