Polycyclic aromatic hydrocarbon (PAH) measurements were conducted by Wood Buffalo Environmental Association (WBEA) at four community ambient Air quality Monitoring Stations (AMS) in the Athabasca Oil Sands Region (AOSR) in Northeastern Alberta, Canada. The 2012 and 2013 mean concentrations of a subset of the 22 PAH species were 9.5, 8.4, 8.8, and 32 ng m–3 at AMS 1 (Fort McKay), AMS 6 (residential Fort McMurray), AMS 7 (downtown Fort McMurray), and AMS 14 (Anzac), respectively. The average PAH concentrations in Fort McKay and Fort McMurray were in the range of rural and semirural areas, but peak values reflect an industrial emission influence. At these stations, PAHs were generally associated with NO, NO2, PM2.5, and SO2, indicating the emissions were from the combustion sources such as industrial stacks, vehicles, residential heating, and forest fires, whereas the PAH concentrations at AMS 14 (∼35 km south of Fort McMurray) were more characteristic of urban areas with a unique pattern: eight of the lower molecular weight PAHs exhibited strong seasonality with higher levels during the warmer months. Enthalpies calculated from Clausius–Clapeyron plots for these eight PAHs suggest that atmospheric emissions were dominated by temperature-dependent processes such as volatilization at warm temperatures. These findings point to the potential importance of localized water–air and/or surface–air transfer on observed PAH concentrations in air.