Polychlorinated biphenyls (PCBs) were widely used in industrial production due to the unique physical and chemical properties. As a kind of persistent organic pollutants, the PCBs would lead to environment pollution and cause serious problems for human health. Thus, they have been banned since the 1980s due to the environment pollution in the past years. Indoor air is the most direct and important environment medium to human beings; thus, the PCBs pollution research in indoor air is important for the protection of human health. This paper introduces the industrial application and potential harm of PCBs, summarizes the sampling, extracting, and analytical methods of environment monitoring, and compares the indoor air levels of urban areas with those of industrial areas in different countries according to various reports. This paper can provide a basic summary for PCBs pollution control in the indoor air environment.