We investigated the concentration and composition of polychlorinated biphenyls (PCBs) in paddy soils and rice tissues and the associated potential health risks in the urban agricultural areas of the Pearl River Delta (PRD), South China. The results indicated that highly chlorinated PCBs were more prominent in soil when the concentrations of low-molecular-weight PCBs were relatively high in rice plants. There was a trend of decreasing PCB concentrations with soil depth and a significant correlation between PCBs and the total organic carbon or total nitrogen concentration in section soils. The PCB concentrations followed the order of root > leaf > stem > grain. Although the dioxin toxicity equivalency values and estimated daily intake levels (based direct and indirect consumption) were lower than in other seriously contaminated regions, there is still a need to monitor PCB pollution in urban agriculture because of the PCB emissions from capacitor storage following the rapid urbanization experienced in the PRD.