In this study, the concentrations of six petroleum hydrocarbons (n-alkane hydrocarbons (total petroleum hydrocarbons [TPH] (C6-C9) and (C10-C40)), BTEX(benzene, toluene, ethylbenzene, m & p-xylene)) in 261 soil, 31 groundwater, and 4 soil gas samples were measured to determine their spatial distribution,migration patterns and human health risks. To assess the rationality of parameter selection, GS-MS (gas chromatography-mass spectrometry) method was used to analyze the chemical composition of TPH (C6-C9), shanghai local regulation was referenced to assess TPH (C10-C40) various segmentation health risks. The results revealed that the contaminants were mainly concentrated in the refining workshop and the storage tank. The pathway of steam invasion in soil gas and the CR (carcinogenic risk) and HQ (hazard quotient) assessment of benzene in soil gas were 0–4 and 1–3 orders of magnitude higher than those in soil. TPH (C6-C9) was more similar to the Total Petroleum Hydrocarbons (Aromatic Low) in RSL (Regional Screening Level). Aliphatic hydrocarbons [AHCs]. (C10-C12) had the highest non-carcinogenic risk among all TPH (C10-C40) parts. The present study provided a reference to accurately determine the toxicological parameters of TPH (C6-C9) and TPH (C10-C40) and to improve the BTEX risk assessment methods.