In a refractory brick manufacturing company a qualitative and quantitative determination of the sources of occupational exposure to polycyclic aromatic hydrocarbons (PAHs) was obtained in order to validate targeted hygiene measurements. The study included the assessment of PAHs contamination of work surfaces by wipe-sampling, cutaneous exposure by hand washing, contamination of personal protective equipments (gloves) by extraction in solvent, and airborne PAHs concentration in atmospheric samples. Biomonitoring was also carried out by measurement of urinary 1-hydroxypyrene (1-OHPU) in three groups of workers (packaging, production, and controls). The surface contamination sampling was performed in production, packaging, and in other departments (external area) in theory less contaminated by PAHs. Two different areas were identified within the production, one included surfaces that were regularly cleaned (A area) and one included data from non-cleaned surfaces (B area). To confirm the source of exposure, a clear correspondence was observed between the percentage of the single compounds in the binder and those measured in wipes and air samples. As far as the wipes are concerned, the concentrations of phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)pyrene (BaP), and the total PAHs mixture were higher in the B area than the A area of production. The same happened between the A area and the other two departments. According to results of the statistical analysis, these differences were significant. These results were confirmed by the hand washing data and the analysis of PPE. On the other hand, a marked difference does not exist between the packaging department and the external area. In air samples, the differences were much less evident with only higher concentrations of anthracene and total PAHs between production as a whole and the other two departments. Biological monitoring showed 1-OHPU values significantly higher in production workers than in packaging workers. In conclusion, the analysis of the wipes demonstrated that the production B area has a higher surface contamination compared to the production A area and the packaging department. In the absence of a significant difference in air concentrations of PAHs between A and B areas, this is attributable to surfaces not subject to cleaning. Results confirm that the measurement of surface contamination represents a valid tool for the assessment of sources of exposure to PAHs in the workplace.