BTEXs are effective reservoir molecule tracing indicators. But low levels of BTEXs in complex matrix samples increase the difficulty of detecting. In this study, a qualitative and quantitative detection method of BTEXs in soil as a geochemical exploration indicator was established using HS-LPME combined with GC/MS. Higher accuracy and precision were obtained. With the advantages of less sample, simple operation, low cost and environmental friendly, this method lays a foundation for its application in surface geochemical prospecting for oil and gas. Results in known oil area showed that there was certain relationship between the toluene concentration in surface soil samples and the underlying oil reservoir. This method was suitable for detection of BTEXs in soil samples in surface geochemical prospecting for oil and gas.