Active sampling was conducted for the first time in Erzurum, Turkey, between August 2012 and January 2013, in order to investigate the presence of 82 polychlorinated biphenyls (PCBs) congeners. Urban and rural ambient air samples, including gas and particle phase atmospheric concentrations (GAPPACs) of PCBs, were collected simultaneously using high volume air sampler (HVAS) at two different sampling points of Erzurum. GAPPACs of PCB samples taken using HVAS in Palandöken Mountain Region (2565m) and Ataturk University Campus (1870m) were analyzed in GC-MS following appropriate extraction steps. Throughout the sampling period, total ambient air concentrations (gas phase + particulate phase) were 10 ± 6 and 27 ± 13pg/m3 (mean) for Palandöken Mountain Region (PMR) and Atatürk University Campus (AUC), respectively. Low molecular weighted PCBs were found to be dominant in both rural an urban sampling sites. Meteorological parameters especially temperature (from Clausius-Clapeyron equation), wind direction, wind velocity, and precipitation were found to be effective on PCB concentration and distribution. The gas-particle distributions of PCBs in the summer and winter period were found to be 82% (gas phase) and 18% (particle phase) in the PMR and 90% (gas phase) and 10% (particle phase) in AUC, through Junge-Pankow adsorption model. In the light of these findings, total PCB concentrations detected in urban atmosphere (due to possible PCB sources) were observed to be higher than those determined in rural area.