The typical biomass fuels in Beijing (made of corn cob, corn stalks, soybean stalks, straw stalks, pine, chestnut branches, peach branches) and civil coal (bituminous coal, honeycomb coal) were selected and combustion experiments were simulated in the laboratory. After collecting particulate matters and gas samples from combustion, organic carbon (OC) and elemental carbon (EC) in different particle size fractions of particulate matter were measured by Model 2001A Thermal/Photocarbon Analyzer, and the VOCs in combustion flue gas were analyzed with Agilent GC-MS 5977/7890B GC-MS as well. The results showed that for honeycomb coal, the emission factor of OC and EC reached the maximum with the particle size of 2.5~10μm, for all the other 8solid fuels, the emission factor of OC and EC were maximum with the particle size of 0~2.5μm. The composition of VOCs from the combustion of these three types of fuels, firewood (chestnut branches, peach branches and pine), straw (corn cob, corn stalks, soybean stalks, straw stalks) and civil coal (honeycomb and bituminous coal), are quite different. The mass fractions of halogenated hydrocarbons and oxygenated organic matter emitted from firewood and civil coal combustion are significantly higher than that from straw type fuels. Within each fuel, VOCs composition is relatively similar. The average total VOCs emission factor was 2.02g/kg for the firewood type, 6.89g/kg for the straws, and 2.03g/kg for the civil coals. VOCs from corn cob, corn stalk, soybean and straw stem have higher ozone formation potential than that from chestnut, peach, pine, bituminous and honeycomb, nonetheless, the composition was similar among the latter group. The VOCs, such as Alkenes, alkanes and aromatic hydrocarbons from solid fuel combustion, were big contributors to the ozone formation potential.