A simple and efficient method based on headspace technique coupled with gas chromatography–mass spectrometry (GC/MS) was developed for the simultaneous determination of four volatile organic sulfur compounds (VOSCs) in surface water samples, including dimethyl sulfide, diethyl sulfide, dimethyl disulfide, and dimethyl trisulfide. Headspace parameters such as sample volume, ionic strength, rotational stirring, headspace analysis duration, and temperature were optimized. The linear range spanned approximately three or four orders of magnitude. The detection limits (MDLs) and method quantification limits were 0.02–0.2 μg/L and 0.06–0.5 μg/L, respectively. The reproducibility (relative standard deviation) of the method was 2.1%–6.5%, and the recovery was 90.0%–114.0%. The method was applied for the determination of VOSCs in surface water, and tap water from four plants for surface water treatment. Only dimethyl sulfide was detected in partial surface water samples (1–7 μg/L), while other VOSCs were all below MDLs.