A headspace（HS） coupled with gas chromatography-mass spectrometric（GC-MS） method was developed for the determination of 5 residual volatile organic compounds（VOCs）in coating samples. The experimental conditions, such as solvent type, equilibrium temperature and time, as well as the analytical conditions of GC-MS, were optimized. The samples were first dissolved in water-N,N dimethylformamide （1∶1, by volume）and treated at 90 ℃ for 90 min,then separated on a DB VRX capillary column（30 m×025 mm×14 μm），and determined by GC-MS with the external standard method. The results indicated that the recoveries were in the range of 82%-105% with relative standard deviations（RSDs） of 05%-39%. The linear range of 5 VOCs were in the range of 0013 3-667 mg/L with correlation coefficient no less than 0998 9. The limits of quantitation （S/N=10） were no more than 10 mg/kg. The method was used to determine 5 VOCs in 22 kinds of solvent based coating and 31 kinds of waterborne coating samples. The result indicated that the proposed method was simple, accurate, rapid and sensitive and could be applied in the rapid analysis of residual VOCs in various coatings.