A headspace technique was developed for the determination of volatile compounds (benzene, toluene, chlorobenzene, ethylbenzene, 1,3‐dichlorobenzene, 1,4‐di‐chlorobenzene and 1,2‐dichlorobenzene) from selected 49 priority pollutants in soil. The headspace sample preparation involved a 20‐mL glass vial containing 3 grams soil and 10 mL of pH 13 spiked solution, equilibrated at 30°C for one hour before 0.5 mL headspace was analyzed by capillary gas chromatography. A reference system was employed at the same time by using 3 grams sand in 10 mL pH 13 spiked solution for the study of the efficiency of the soil headepace analysis. Once the recovery rote between the soil and the reference system is established, the ratio can be used for the determination of other soil samples from the same origin. The relative standard deviation for 3 grams soil sample spiked with 5.1 ppm (51μg / 10 mL.) pollutant mixture in a 20 mL viol is less than 3%.