In recent years, China suffered from extensive air pollution due to the rapidly expanding economic and industrial developments. Its severe impact on human health has raised great concern currently. Persistent toxic substances (PTSs), a large group of environmental pollutants, have also received much attention due to their adverse effects on both the ecosystem and public health. However, limited studies have been conducted to reveal the airborne PTSs associated with air pollution at the national scale in China. In this review, we summarized the occurrence and variation of airborne PTSs in China, especially in megacities. These PTSs included polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), halogenated flame retardants (HFRs), perfluorinated compounds (PFCs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and heavy metals. The implication of their occurrence associated with air pollution was discussed, and the emission source of these chemicals was concluded. Most reviewed studies have been conducted in east and south China with more developed economy and industry. Severe contamination of airborne PTSs generally occurred in megacities with large populations, such as Guangzhou, Shanghai and Beijing. However, the summarized results suggested that industrial production and product consumption are the major sources of most PTSs in the urban environment, while unintentional emission during anthropogenic activities is an important contributor to airborne PTSs. It is important that fine particles serve as a major carrier of most airborne PTSs, which facilitates the long-range atmospheric transport (LRAT) of PTSs, and therefore, increases the exposure risk of the human body to these pollutants. This implied that not only the concentration and chemical composition of fine particles but also the absorbed PTSs are of particular concern when air pollution occurs.