A repeated measurement cohort study was conducted to determine whether 2-napthol can be a suitable biomarker for evaluating the magnitude of exposure to PAHs from coke oven emissions. Time-course patterns of urinary 2-naphthol levels in coke-oven workers were examined. Also, the correlation between urinary 2-naphthol levels and PAHs from personal breathing zone samples was analyzed while examining and adjusting possible confounding factors, such as smoking alcohol consumption, and age of human subjects. A total of 8 spot urine samples were collected from each high-exposure group (topside-oven workers, n = 17) and low-exposure group (side-oven workers, n = 25) during the whole working cycle, which consists of six consecutive working days followed by 2 days off. Personal breathing zone samples were collected to quantify PAH intake. A questionnaire was distributed and collected from each worker for assessment of demographic parameters. Our results confirmed that the topside-oven area contained significantly higher PAH levels than the side-oven area. Urinary 2-naphthol levels correlated with the levels of PAH species, including pyrene, benzo[k]fluoranthene, benezo[g,h,i]pyrene, naphthalene, phenanthrene, anthracene, indeno[1,2,3-cd]pyrene, benzo[k]fluoranthene, and total PAHs. During the working cycle, urinary 2-naphthol levels remained stable at around 46-97 ng/mg creatinine during the working days and dramatically increased during the off days. After stratification of data based on smoking status, smokers had significantly higher urinary 2-naphthol levels than non-smokers, and 2-naphthol levels positively correlated with smoking status. Coke-oven emissions are a source of exposure to naphthalene. Also, smoking is a significant source of exposure to naphthalene and served as a confounder factor. Due to its abundance, positive association with total PAHs and certain carcinogenic PAH compounds, and slower elimination kinetics, urinary 2-naphthol may have the potential to serve as a biomarker for PAH exposure, when smoking status is carefully adjusted.