Field measurements were conducted to determine indoor air particulate pollutant emissions from the burning of coal and wood, two major household fuels, in rural households in Guizhou, China. Chemical composition, particle mass and particle size distribution as well as number concentration were measured in this study. Chemical composition analysis indicates that the carbonaceous particle is dominant in the PM2.5 mass, accounting for about 41% for wood and 55% for coal. The OC/EC ratio was 10.8 for wood and 7.6 for coal. Most of the water-soluble ions were found in the 0.4–2.1 μm size fractions and dominated by ammonium and sulfate. Particle mass concentrations inversely correlate with particle total number concentrations during the sampling period. Obvious differences were observed in the evolution of particle number concentrations and size distributions between coal combustion and wood burning. Particles emitted from coal combustion were characterized by unimodal size distribution, with average peak values ranging from 70.3 to 75.7 nm during the flaming stage of the burning cycle. Particles from wood burning were characterized by a transition from a bimodal size distribution to a unimodal distribution during the same period. Average peak values in the bimodal mode were 10–20 nm (nucleation mode) and 40–50 nm (Aitken mode), whereas the average peak value in the unimodal mode was about 63 nm.