Firefighters and asphalt pavers are exposed to polycyclic aromatic hydrocarbons (PAHs) during various work activities. The purpose of this study was to evaluate urinary PAH levels and compare these bio-monitoring levels among firefighters, asphalt pavers, and non-occupationally exposed individuals. The National Institute of Standards and Technology (NIST) urinary PAH levels were used for non-occupationally exposed controls. When compared to the NIST standard for smokers and non-smokers, firefighters demonstrated statistically significant differences in urinary concentration differences for the following metabolites: 2-OH-fluorene, 3-OH-fluorene and 1-OH-pyrene, which were lower in firefighters than the NIST mean for smokers. 1-OH-phenanthrene, 2-OH-phenanthrene and 3-OH-phenanthrene were higher among world trade center exposed firefighters than the NIST mean for smokers. When firefighters were compared to the NIST non-smoker standard, firefighters demonstrated elevated levels in all tested PAH biomarkers due to a mixture of smokers and non-smokers in the firefighter cohort. Asphalt workers had statistically significant higher urinary concentration elevations in 2-OH-fluorene, 1-OH-phenanthrene and 3-OH-phenanthrene as compared to the NIST smoker mean. When asphalt pavers were compared to the NIST non-smoker mean, asphalt pavers had statistically significant increases in all tested PAH biomarkers, with the exception of 2-OH-phenanthrene. While firefighters did not demonstrate a substantial change in urinary PAH metabolite levels compared to control populations of smokers and non-smokers, asphalt pavers experienced concentrations that were in some cases increased by orders of magnitude compared to NIST controls. Future research may be needed to evaluate any potential health risk posted to occupational exposed asphalt pavers.