Polycyclic Aromatic Hydrocarbon (PAHs) were determined in outdoor organic films formed on window glasses inside a street canyon at four different heights. The vertical distribution of PAHs in the organic film and the factors responsible for this have been studied. Significant changes of the concentration levels depending on the height and on the season were observed. The concentrations were elevated in the organic film at the street level and during the cold period. This work provides evidences that window organic film may pose an additional risk for human health in such locations through the accumulation of PAHs near the street level.