Anhui Province is the most important energy production base for eastern China. Many large pithead coal-fired power plants are being operated in the coal-rich Huainan and Huaibei coalfields in northern Anhui. To assess the environmental risks of local coal-fired power plants, a complete atmospheric emission inventory of F, As, Se, Cd, Sb, Hg, Pb, and U from coal-fired power plants in Anhui was compiled by a simple mass-balance-based method. The results indicated that the atmospheric emissions of F, As, Se, Cd, Sb, Hg, Pb, and U in 2017 from the Anhui coal-fired power plants were 578 t, 2.01 t, 15.3 t, 0.57 t, 0.18 t, 2.80 t, 23.7 t, and 0.099 t, respectively. The emission factor is the major contributor to the uncertainties in this inventory. With increasing energy demand by the more developed eastern China region, the atmospheric emissions of volatile hazardous elements will continue to increase in the near future.