Coal, fly ash and bottom ash samples were taken from a 300-MWe coal-fired power plant with a daily coal consumption of 2400 tons. A high volume sampler coupled with several mesh testing sieves was used to separate fly ash samples into different size fractions. Determination of the concentrations of 40K, 238U, 226Ra, 210Pb, 210Po, 228Th and 228Ra was carried out either by gamma or alpha spectrometry. For elements volatilized during combustion, their radionuclide concentrations decrease with increasing particle size. The enrichment factors for all radionuclides mentioned above were studied. Their values range from 31.0 for 210Po to 2.2 for 228Ra. Of all radionuclides studied, 210Po and 210Pb are the most volatile elements; therefore, an increase in the natural radiation level should first be indicated by an increase in these two nuclides.