The Chinese Gridded Industrial Pollutants Emission and Residue Model (ChnGIPERM) was used to investigate potential fractionation effects and atmospheric transport of polychlorinated biphenyls (PCBs) derived from single-source emissions in China. Modeling the indicative PCBs (CB28, CB101, CB153, and CB180) revealed spatiotemporal trends in atmospheric transport, gas/particle partitioning, and primary and secondary fractionation effects. These included the inference that the Westerlies and East Asian monsoons affect atmospheric transport patterns of PCBs by influencing the atmospheric transport time (ATT). In this study, dispersion pathways with long ATTs in winter tended to have short ones in summer and vice versa. The modeled partitioning of PCB congeners between gas and particles was mainly controlled by temperature, which can further influence the ATT. The potential for primary and secondary fractionation was explored by means of numerical simulations with single-source emissions. Within ChnGIPERM, these phenomena were mainly controlled by the temperature and soil organic carbon content. The secondary fractionation of PCBs is a slow process, with model results suggesting a timescale of several decades.