Evidence suggests that people living in urban areas have an increased risk of lung cancer due to higher levels of air pollution in these areas. Benzo[a]pyrene (B[a]P) is currently used as the main indicator of carcinogenic polycyclic aromatic hydrocarbons (PAHs) in air pollution, but there is concern that B[a]P may not be the ideal surrogate of choice for PAH mixtures since higher potency PAHs have recently been identified which could potentially contribute more and variably to the overall carcinogenicity. Dibenzo[a,h]anthracene (DBA) and dibenzo[a,l]pyrene (DB[a,l]P) are estimated to have carcinogenic potencies 10 or more times greater than B[a]P but data on their presence and formation in the environment are limited. Several occupational and environmental PAH biomonitoring studies are reviewed here, with particular focus on the specific exposure groups, study design, sample tissue, in particular the use of nasal tissues, and biomarkers used in each study. Consideration of these data is then used to propose a novel biomonitoring approach to evaluate exposure, uptake and the role of high potency PAHs in air pollution-related lung cancer. This is based upon an occupational study examining specific DNA adducts for DBA and DB[a,l]P in nasal cells to evaluate the extent to which these high potency PAHs might contribute to the increased risk of developing lung cancer from air pollution.