To monitor and evaluate the risk of polychlorinated biphenyls (PCBs) contamination in Pohang, Korea, the concentration and distribution of 29 PCBs in paddy soils were determined using high-resolution gas chromatography/high-resolution mass spectrometry. The overall concentrations of Σ29 PCBs in the paddy soils of the areas close to the heavily industrial city of Pohang (268–1833 pg g−1 dw) were higher than those in the paddies from Anseong (106.6–222.6 pg g−1 dw) in Korea. In Pohang, the major contributors to the Σ29 PCBs were the non-dioxin-like PCBs, including the PCBs 28, 52, 70, 101, 118, 138, 153, and 180, which correspond to 48–62% of the total PCBs. The toxic equivalency (TEQ) values obtained from the 12 dioxin-like PCBs from Pohang (0.03–1.03 pg TEQ g−1 dw) showed that PCB 126 contributed the highest toxicity, possibly posing a risk to the living organisms. The results of both principal component and cluster analysis based on the PCB homologue patterns demonstrated that each sampling site showed a similar PCBs contamination pattern, and Aroclor 1254, which is likely used by small and big steel factories, was identified as a major source of PCB contamination in Pohang.