The present study was undertaken to evaluate the occupational exposure to PAHs of long-term workers in a specific petroleum refinery in Albania. The main route of exposure to these pollutants is via inhalation within a highly contaminated work environment. Serum samples from workers were collected and analyzed. A cloud-point extraction method was applied to isolate and concentrate PAHs from samples using Triton X-100 as the extraction agent. The phase separation of micellar serum solutions was induced with the addition of sodium chloride. The analyses were performed by gas chromatography/mass spectrometry using a capillary column HP-5MS. The PAHs analyzed were acenaphthene, acenaphthylene, anthracene, benzo[α]anthracene, benzo[α]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[g,h,i]perylen, chrysene, dibenzo[α,h]anthracene, fluorene, indeno [1,2,3-cd]pyrene, naphthalene, phenanthrene and pyrene. Mean concentration of analytes ranged from 4 ng mL−1 for fluorene and anthracene to 110 ng mL−1 for dibenzo[α,h]anthracene. The compositional profile of the PAHs was primarily 4–6 rings PAHs. Diagnostic isomeric ratios of benzo[α]anthracene/(benzo[α]anthracene + chrysene) and phenanthrene/anthracene suggest that the PAHs in the serum were primarily pyrogenic PAHs. The bioaccumulation trend of the PAHs in the workers proved conditional to their physical location within the workplace.