Coal is one of the major energy resources in China, with nearly half of produced Chinese coal used for power and heat generation. The large use of coal for power and heat generation in China may result in significant atmospheric emissions of toxic volatile trace elements (i.e. F, As, Se, Hg, and Sb). For the purpose of estimating the atmospheric emissions from coal-fired power and heat generation in China, a simple method based on coal consumption, concentration and emission factor of trace element was adopted to calculate the gaseous emissions of elements F, As, Se, Hg, and Sb. Results indicate that about 162161, 236, 637, 172, and 33 t F, As, Se, Hg, and Sb, respectively, were introduced into atmosphere from coal combustion by power and heat generation in China in 2009. The atmospheric emissions of F, As, Se, Hg, and Sb by power and heat generation increased from 2005 to 2009 with increasing coal consumptions.