Background and Objective: Petrochemical industries are known as one of the most important sources of organic pollutants which endanger the workers' health. The aim of this study was to evaluate the relationship between inhaled Benzene, Toluene, Ethylbenzene, and Xylene (BTEX) concentrations and some urine metabolites of people working at a petrochemical complex. Materials and Methods: This cross-sectional study was an analytical type with 60 inhalation air samples and biological samples. Sampling and decomposition of pollutants were carried out in accordance with 1501 and 2549 methods of National Institute for Occupational Safety and Health (NIOSH). The results then were compared with the Occupational Exposure Scale (OEL) and the proposed National Occupational Exposure Indicators (BEI) in Iran. Statistical analysis was performed in SPSS software (version 17). Results: The results of the study showed that the mean concentration of Trans, Trans-muconic acid (TTMA) was 137μ g/g Creatinine. The concentrations of Hyporic acid, Phenylglyoxalic acid, and Methyl-hyporic acid were obtained as 0. 577, 0. 066, and 0. 404 g/g Creatinine, respectively. In addition, the mean concentration of benzene, toluene, ethylbenzene, o-, mxylene, and p-xylene were 3. 818, 4. 004, 3. 357, 0. 132, and 2. 0159 ppm, respectively. The results also showed that toluene and benzene concentrations in 5 inhalable samples and Hyporic acid and TTMA in 10 urine samples were higher than the proposed limit. Conclusion: The mean total concentration of inhaled BTEXs and the urine metabolites were lower than the acceptable range recommended by the country. There is a high correlation between measured pollutants in respiratory air and the concentration of urine metabolites. Therefore, it can be concluded that the chronic exposure to these pollutants leads to an increase in the excretion of urine metabolites. As well, the working conditions have detrimental effects on the health of people encountering with these organic compounds.