The work aims to establish a method for determination of four residual solvents in offset printing fountain solution. CD-VOCOL column (60 m×0.32 mm×1.8 μm, CNW) was used to determine the residues of methanol, ethanol, iso-propyl alcohol and cyclohexanone in offset printing fountain solution by means of HS/GC-MS. After four residual solvents were effectively separated, the correlation coefficient was more than 0.998 and the recovery rate was 87.5%～102.5%. Easy and simple to operate, and having accurate results with good reproducibility, the proposed method can meet the needs of practical analysis.