A simple method for qualitative and quantitative determination of PCB95, 132, 149 and 174 enantiomers in soils and sediments using GC-ECD/MS was proposed. On the promise of good purification efficiency, high recovery and easy operability, H2SO4 washing and a multi-layer column filled with 1 g anhydrous sodium sulfate, 2 g 10% silver nitrate-impregnated silica gel, 4 g 3.3% water-deactivated silica gel and 1.5 g anhydrous sodium sulfate were selected as purification procedures. The chromatographic conditions were optimized to obtain the best enantiomeric separation. Complete baseline separations were achieved for PCB95, 132 and 149, as well as approximate baseline separation was obtained for PCB174. This method was proved to have highly satisfactory accuracy, precision and sensitivity with mean recoveries of target PCB enantiomers in range of 71.42−80.12% and RSD<6%. The detection limits of the method were 11.37−25.36 pg•g−1.