Polychlorinated biphenyls (PCBs) were widely used in industrial and commercial applications, until they were banned in the late 1970s as a result of their significant environmental pollution. PCBs in the environment gained scientific interest because of their persistence and the potential threats they pose to humans. Traditionally, human exposure to PCBs was linked to dietary ingestion. Inhalational exposure to these contaminants is often overlooked. This review discusses the occurrence and distribution of PCBs in environmental matrices and their associated health impacts. Severe PCB contamination levels have been reported in e-waste recycling areas. The occurrence of high PCB levels, notably in urban and industrial areas, might result from extensive PCB use and intensive human activity. Furthermore, PCB contamination in the indoor environment is ten-fold higher than outdoors, which may present expose risk for humans through the inhalation of contaminated air or through the ingestion of dust. In such settings, the inhalation route may contribute significantly to PCB exposure. The data on human health effects due to PCB inhalation are scarce. More epidemiological studies should be performed to investigate the inhalation dose and response mechanism and to evaluate the health risks. Further studies should also evaluate the health impact of prolonged low-concentration PCB exposure.