A headspace gas chromatography (HSGC) method was established for the determination of residual methanol, isopropanol, methyl ethyl ketone, ethyl acetate and isobutanol in sucrose fatty acid esters. Samples were directly injected into the headspace. The chromatographic analysis was performed on a DB-1 column (60 m × 530 μm, 1 μm) equilibrated for 40 min at 80 ℃. The results showed that the calibration curves for the five solvents were linear in the range of 0.05–10.00 μg, with correlation coefficients greater than 0.999, and the limits of quantitation (LOQ) for methanol, isopropanol, methyl ethyl ketone, ethyl acetate and isobutanol were 0.024 4, 0.019 7, 0.022 7, 0.024 5 and 0.019 2 mg/kg, respectively. The average recoveries for all analytes were in the range from 81.7% to 96.8%, and the relative standard deviation (RSD) for precision ranged from 1.90% to 4.52%. The pretreatment method was simple and rapid, with good recovery and precision, and was suitable for the analysis of the five residual solvents in sucrose fatty acid esters. A total 20 lots of of sucrose fatty acid ester samples were detected by the proposed method. The residues of three solvents in 17 of them met the requirements of the Joint FAO/WHO Expert Committee on Food Additives (JECFA). The detection rate of methanol was highest (80%), and methanol was the major solvent retained in the lipophilic samples at a level up to 9.42 mg/kg. More solvents were detected in the hydrophilic samples at lower levels.