Pervaporation has been coupled on-line to capillary electrophoresis (CE) by a simple interface consisting of a modified CE vial. The approach allows volatile analytes to be removed and injected into the capillary meanwhile the sample matrix remains in the pervaporator. By this approach volatile acidity and free sulfur dioxide have been simultaneously determined in wines. The detection limits (LODs) are 1.25 and 5.00 mu g/mL, the quantification limits 4.12 and 16.50 mu g/mL, and the linear dynamic ranges between LOD and 50 mu g/mL and between 0.1 and 0.9 g/L for free sulfur dioxide and volatile acidity, respectively. The repeatability and within laboratory reproducibility, expressed as relative standard deviation (RSD), are 1.61% and 3.00% for free sulfur, and 3.35% and 4.58% for volatile acidity, respectively. The optimal pervaporation time and the time necessary for the individual separation-detection of the target analytes are 6 and 5 min, respectively. The analysis frequency is 7 h(-1) and the sample amount necessary is less than 7 mL. The proposed method and official methods for the analytes were applied to 32 wine samples. A two-tailed t-test was used to compare the methods, which yielded similar results. The errors, expressed as RSD for the two parameters, ranged between 1.3 and 4.1%.