This work presents the results of the first Serbian monitoring campaign performed to assess the occupational exposure of petrochemical industry workers to benzene (B), toluene (T), ethylbenzene (E), and xylene (X), known collectively as BTEX. The following urinary biomarkers were investigated: phenol, hippuric acid, o-Cresol, p-Cresol, and creatinine. BTEX compounds were collected in 2014 using Casella passive samplers. Multivariate statistical analysis was performed to put in evidence the correlation between the BTEX measured in air and the concentration of urinary biomarkers. While the results indicate an elevated presence of benzene in the air in the working environment studied that surpasses the national and European Occupational Exposure Limits (OEL), the levels of the remaining (TEX) parameters measured were below the OEL. The high relative standard deviations (RSD) for the concentrations of each BTEX compound (68–161 mg m−3) point toward an intensive occupational exposure to BTEX. This was confirmed by relevant urine biomarkers, particularly by the mean values of phenol, which were ten and fourteen times higher than the ones found in the control group (14–12 mg g−1 of creatinine). On average, workers are at a higher risk of developing cancer (6.1 × 10−3), with risk levels exceeding the US EPA limits. Benzene levels should therefore be maintained under tight controls and monitored via proper urinary biomarkers.