The source and environmental behavior of dioxin-like polychlorinated biphenyls (PCBs) together with other PCBs and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs) were evaluated based on analysis of variations in their atmospheric concentrations in Yokohama, Japan. Potential factors responsible for variations in the atmospheric concentrations of the congeners were investigated by principal component analysis and multiple regression analysis of the data. Two major variations were seen: one had strong temperature dependence, while the other had no significant temperature dependence. A possible explanation for this difference is that the former is related to congeners released by volatilization (e.g., volatilization from commercial PCB products and past polluted environments), while the latter is related to congeners emitted from thermal processes. The relative contributions of dioxin-like PCBs released by volatilization and those emitted from thermal processes were estimated based on the temperature dependence of the atmospheric concentrations. The results suggest that both dioxin-like PCBs emitted from thermal processes and those released by volatilization are significant sources of air pollution in this area in terms of the toxic equivalent (TEQ) for dioxin-like PCBs. We demonstrated that the present approach based on variations in atmospheric concentrations can be useful in providing a qualitative as well as quantitative understanding of source information.