Headspace solid-phase microextraction was applied to gas chromatography coupled to flame photometric detection to develop a method for analysing volatile sulphides and disulphides in wine. The Carboxen-polydimethylsiloxane-coated silica fiber was tested and different parameters such as presampling time, ionic strength, stirring, headspace volume, ethanol concentration, time and temperature of extraction were optimized to make extraction as efficient as possible. The optimized conditions enabled limits of detection to be obtained at the ng/l levels. The fiber tested has a strong affinity for the sulphur compounds studied and enables these analytes to be quantitatively determined in wines. The Carboxen-polydimethylsiloxane-coated fiber is more efficient at extracting than fibers such as those which are polydimethylsiloxane-coated and polyacrylate-coated, but its repeatability is worse. The overall process was successfully applied to identify and quantify sulphur compounds in white, red, rose and vintage wines.