Abstract: Objective To investigate human internal exposure levels and composition of polycyclic aromatic hydrocarbons (PAHs) in urine of residents living around a petrochemical enterprise. Methods According to continuous random variables sampling method, urine samples from residents living around a petrochemical enterprise in South China were collected in July 2012. The hydroxyl-PAHs (OH-PAHs) in the urine samples were detected by the rapid liquid chromatography coupled to triple quadrupole tandem mass spectrometry. Results A total of 165 residents (81 males and 84 females) aged 45 and over were investigated. Among the residents, 102 (62.82%) were aged 45 to 64 years. Their occupation was mainly farmer (49.09%, 81/165). Ten OH-PAHs detected in the urinary samples and their median concentrations of the metabolites were 2-hydroxy naphthalene (1.83μmol/mol creatinine),1-hydroxy naphthalene (1.34),2-+3-hydroxy fluorine (0.51),2-hydroxy phenanthrene (0.14),3-hydroxy phenanthrene (0.21),4-hydroxy phenanthrene (0.07), 1-+9-hydroxy phenanthrene (0.69) and 1-hydroxy pyrene (0.25)．Except 2-OHN and 1-+9-OHPhe, the other OH-PAHs were positively correlated (P<0.05 or P<0.01) and the correlation coefficients ranged from 0.20 to 0.76. Conclusion OH-PAHs in urine samples of residents living around the petrochemical enterprise were dominated by total hydroxyl naphthalene (1-OHN and 2-OHN), which was consistent with the fact that the main pollutants of the petrochemical factory were low ring OH-PAHs.