Polycyclic aromatic hydrocarbons (PAHs) are toxic and hazardous volatile environmental pollutants that have been studied as possible major causative agents of lung cancer in Xuanwei. In this paper, indoor and outdoor PM2.5 samples were collected from two homes at different time periods in Hutou, the lung cancer epidemic area in Xuanwei. The results showed that PAH pollution levels from coal combustion in Xuanwei lung cancer epidemic area were significant. The mass concentrations of total PAHs, major carcinogenic compounds, and benzo[a]pyrene-based equivalent concentration (BaPeq) were significantly higher in the coal-using home than in the electricity-using home. For the coal-using home, the PAHs were mainly derived from coal combustion. For the electricity-using home, the PAHs might have been a combination of traffic and coal combustion sources. The human health risk due to inhalation exposure to the PAHs was represented by the incremental lifetime cancer risk (ILCR) of the inhalation exposure. The results showed that the indoor cancer risk for the coal-using home in Xuanwei is higher than that of the electricity-using home and much higher than that of Chinese megacities such as Beijing and Tianjin. Long-term exposure to indoor coal-burning environments containing high levels of PAHs may be one of the main reasons for the high incidence of lung cancer in Xuanwei.