Often, the sources of polycyclic aromatic hydrocarbons (PAHs) in environmental media can be identified by comparing the ratios of concentrations of selected pairs of PAH congeners in the source emissions to the ratios in the contaminated environmental media. However, these ratios can be altered significantly due to differences in the transport of the PAH compounds in a multimedia environment. To examine such changes, a fugacity model was applied to PAH ratios in a model environment. A linear relationship between the rate of emission and the bulk media concentration was identified for each PAH compound in an environmental medium at steady state and was quantified by a receptor-to-source ratio (RRS). It was demonstrated that the RRS values of the two congeners usually differ significantly. Consequentially, PAH ratios changed remarkably from the source emissions to various environmental media. A site-specific rectification factor (RF) was defined as the ratio of the two RRS values of the paired congeners for a specific PAH ratio in a given medium, which can be applied to account for the ratio changes in a multimedia environment. The PAH ratio changes were further verified with the surface soil data collected from Tianjin, China, and the observed changes of PAH ratios were compared favorably with the model predictions. The sensitivity analysis revealed that PAH ratios of the low molecular weight compounds were less stable. The most influential parameters controlling PAH ratios were those pertaining to dry precipitation, surface-to-air diffusion, degradation in air and water, and exchange between water and sediment.