This paper introduced the method used to measure 222Rn emanation coefficients of coals and its solid waste: fly ashes and slag. The results show that the emanation coefficients of coal samples have nothing to do with its specific activity of 226Ra, but are under the influences of humidity and particle size. Structure and morphology changes create an influence on the emanation coefficients of fly ashes and slag, as they are formed after high temperature combustion. The results also show that the emanation coefficient of coals is 7~10 times of th...