The existing volatile organic compounds (VOCs) sampling standards are mostly for simple environments and small molecular compounds,and lack sampling methods for coal-fired flue gas with high humidity,high dust and complex composition. Based on the existing sorbent adsorption-thermal desorption-gas chromatography mass spectrometry sampling standard HJ 734—2014 "Stationary source emission-determination of volatile organic compound-sorbent adsorption and thermal desorption gas chromatography mass spectrometry method"，five kinds of VOCs including acetone,hexane,toluene,ethylbenzene,and 1-decylene,and coal-fired simulated flue gas were sampled by the improved sampling system to investigate the effects of different sorbents,moisture and other flue gas components on VOCs sampling and analysis. The results show that the adsorbent tubes filled with porous polymer adsorbent (Tenax TA) and sulfur molecular sieve adsorbent (Sulficarb) have relative standard deviations of 0.01%-2.04%,and standard average recoveries are more than 80%,which are more suitable for the sampling of VOCs from coal combustion. The ash removal device or water removal device in the sampling system has little impact on VOCs,which can ensure the accuracy and effectiveness of the data in the sampling process. Without the sampling system,the presence of moisture,NO and SO2 in the simulated flue gas can have a negative impact on the average and weight recovery rate of VOCs,among which 1-decene is greatly affected by the flue gas environment and the average recovery rate only reaches 36%. When the mass concentrations of NO and SO2 vary from 16 to 621 mg/m3 and 40 to 1 326 mg/m3,respectively,the sampling system can well reduce the impact of moisture,NO and SO2 on the simulated flue gas,which can provide a reference for the sampling in actual coal-fired power plants.