A method for simultaneous determination for 23 volatile chlorinated hydrocarbons and benzene series in soil samples by gas chromatography-mass spectrometry (GC-MS) with purge and trap pretreatment is introduced. The conditions of purge and trap, the qualification of GC-MS, and the centrifuge are confirmed. Under the best conditions, the liner range of the standard curve is 0.32~200.0 μg/kg. The detection limits range of the method for the 23 volatile organic compounds are 0.077~0.69 μg/kg. The average recoveries are 86.5% to 117.5%, with precision of 1.6%~8.2 % (n = 7). This fast and accurate method can be applied to determinate the 23 volatile organic compounds in batch soil samples with satisfactory results.