To strengthen regulation for mitigating the risk posed by petroleum contaminants in soil, the Ministry of Ecology and Environment of the People's Republic of China has classified petroleum hydrocarbons as a key monitoring item for regulatory contamination monitoring. Petroleum is principally derived from petroleum and synthetic fuels, which contain an extremely high content of hydrocarbon compounds that have varied boiling points. These compounds are chemically classified primarily as saturated and aromatic. Aromatic hydrocarbons are typically highly alkylated monocyclic, bicyclic, and polycyclic, which are more toxic to human and animal life than saturated hydrocarbons. Because of the significant toxicological differences among the various hydrocarbons, it is difficult to accurately assess their environmental toxicity by only determining the total content of petroleum in soil. However, there are no analytical methods for the simultaneous determination of saturated hydrocarbons and aromatic hydrocarbons in soil according to Chinese standards. In this study, extraction and purification procedures were completely optimized depending on the matrix of the soil samples. The advanced analytical technique of on-line high performance liquid chromatography-gas chromatography (HPLC-GC) was performed after sample preparation for the simultaneous determination of saturated hydrocarbons and aromatic hydrocarbons in soil. For the extraction, n-hexane/ethanol (1∶1, v/v) was chosen as the extraction solvent. The ratio of solid sample (soil) to the solvent was chosen as 1∶4, and extraction was performed once at room temperature, for 1 h. Water was then added and mixed to remove ethanol from the extracts, and the upper n-hexane layer was separated; thus, the petroleum hydrocarbons in the samples were completely extracted. However, the oils and fats in the matrix of the soil sample were also simultaneously extracted. Because of the limited retention capacity of the HPLC column, the presence of oils, fats, and other interferents would affect the subsequent determination of saturated hydrocarbons and aromatic hydrocarbons. Therefore, an additional purification step is required before sample injection into the HPLC-GC equipment. In this study, purification was performed using a lab-made silica gel column, which is commonly used for the determination of saturated hydrocarbons and aromatic hydrocarbons in food. The purification column was conditioned and eluted with an 8∶2 ratio (v/v) of n-hexane to dichloromethane after sample loading. Subsequently, the eluent was concentrated and injected into the HPLC-GC equipment for analysis. The flame ionization detector (FID) is ideal for petroleum hydrocarbons quantification because of its nearly identical responses to all hydrocarbons; hence, with the FID, reference standards are not required for quantification, and internal standards are typically used for quantifying the total hydrocarbon content. In this study, cyclohexylcyclohexane (Cycy) and 2-methylnaphthalene (2-MN) were used as internal standards for determining the saturated and aromatic hydrocarbons, respectively. The limit of quantification (LOQ) of this proposed method was 0.4 mg/kg. Moreover, the suitability of the method was verified by comparing the obtained content against the soil petroleum hydrocarbon standard (SQC-116); the measured value was found to be within the credible interval provided by the standard. The relative error (RE) was 10.6% with a relative standard deviation (RSD) of 1.4%, which indicates that the proposed method is accurate and reliable, and the precision meets analytical requirements. Finally, the method was applied to the determination of hydrocarbons in five soil samples from the Beijing area. Saturated hydrocarbons (C10-C40) were detected in all five samples, with contents ranging from 3.3 to 32.1 mg/kg, while aromatic hydrocarbons (C10-C40) were detected in four samples, with contents ranging from 0.8 to 4.3 mg/kg. HPLC-GC combines the high selectivity of HPLC with the high separation efficiency of GC, and as demonstrated in this study, can be used for the simultaneous determination of saturated and aromatic hydrocarbons in soil. The source of hydrocarbon contamination can also be preliminarily identified by chromatographic analysis.