Dimethyl sulfides are ubiquitous odorous substances in eutrophic freshwater bodies. In this study, a simple headspace solid-phase microextraction-gas chromatography-flame photometric detection method was developed to detect three representative algal-derived dimethyl sulfides in freshwater lake water samples: dimethyl monosulfide (DMS), dimethyl disulfide (DMDS), and dimethyl trisulfide (DMTS). The effects of extraction fiber, temperature, pH, ionic strength, and sample volume were investigated orthogonally, and the optimized method was applied to analyze surface water samples from Lake Ulansuhai in Inner Mongolia, China. Optimal extraction was obtained with a 50/30 µm DVB/CAR/PDMS extraction fiber, 20% ion concentration, 87 min extraction time, and 50 °C extraction temperature. The correlation coefficients of the standardized working curves for DMS, DMDS, and DMTS were 0.9967, 0.9907, and 0.9994, respectively, indicating good linear relationships. Limits of detection were in the nanogram range, and the recoveries of the spiked standards for DMS, DMDS, and DMTS were 97.22~99.07%, 93.39~99.34%, and 91.17~99.25%, with relative standard deviations of 5.18~5.94%, 3.08~6.25%, and 2.56~5.47%, respectively. This method is stable and reliable, and can be used for the determination of volatile sulfides in freshwater lake water.