A method has been developed for separation and determination of benzene, toluene, m-xylene and o-xylene using 0.25 mm×30 m×0.5 μm high efficiency quartz capillary column by ourselves with PEG-20M (polyethylene glycol-20000).In the benzene hydrocarbon there are some non-aromatic hydrocarbon impurities which will disturb the analytical resuer. If polar capillary column was preferred, the retention time of aromatic hydrocarbon delays greatly and that of non-aromatic hydrocarbon shortens. The three xylene isomers were separated clearly. This method is obviously surperior to the GB/T3144-82. The advantage of this method lies in its high speed and good separation.