Air samples were collected simultaneously at three sites downwind of Lake Ontario and at a control site near Lake Erie from March to July of 1999. The Lake Erie site (Stockton, NY) had PCB concentrations similar to rural Integrated Atmospheric Deposition Network (IADN) sampling sites across the Great Lakes, exhibited limited seasonal variation, and approximates regional background. Samples taken along Lake Ontario's southeastern shore (Rice Creek and Sterling, NY) had elevated PCB concentrations averaging approximately 1 ng/m3 and were more chlorinated than air collected at IADN sites and at Stockton. Air samples from Potsdam (approximately 75 km inland) had similar concentrations but were less chlorinated. Clausius-Clapeyron plots revealed a strong correlation between PCB fugacity and temperature near Lake Ontario; however, the extent of chlorination of the air samples rules out volatilization from the lake as a major source. It is hypothesized that volatilization from local surfaces, enriched in higher chlorinated congeners by meteorological or geographic factors, drives both the concentration and composition of airborne PCBs along Lake Ontario's southeastern shore.