Polyethylene passive sampling was applied to quantify gaseous and freely-dissolved polychlorinated biphenyls (PCBs) in the air and water of Lakes Erie and Ontario during 2011-2012. In view of differing physical characteristics and the impacts of historical contamination by PCBs within these lakes, spatial variation of PCB concentrations and air-water exchange across these lakes may be expected. Both lakes displayed statistically similar aqueous and atmospheric PCB concentrations. Total aqueous concentrations of 29 PCBs ranged from 1.5 pg L-1 in the open lake of Lake Erie (site E02) in 2011 spring to 105 pg L-1 in Niagara (site On05) in 2012 summer, while total atmospheric concentrations were 7.7-634 pg m-3 across both lakes. A west-to-east gradient was observed for aqueous PCBs in Lake Erie. River discharge and localized influences (e.g., sediment resuspension and regional alongshore transport) likely dominated spatial trends of aqueous PCBs in both lakes. Air-water exchange fluxes of Σ7PCBs ranged from -2,420 (±1,870) pg m-2 day-1 (deposition) in Sheffield (site E03) to 9,030 (±3,070) pg m-2 day-1 (volatilization) in Niagara (site On05). Net volatilization of PCBs was the primary trend across most sites and periods. Almost half of variation in air-water exchange fluxes was attributed to the difference in aqueous concentrations of PCBs. Uncertainty analysis in fugacity ratios and mass fluxes in air-water exchange of PCBs indicated that PCBs have reached or approached equilibrium only at the eastern Lake Erie and along the Canadian shore of Lake Ontario sites, where air-water exchange fluxes dominated atmospheric concentrations. .