Fine particles formed from combustion of a bituminous coal and co-combustion of coal with 7 th% (thermal percentage) solid recovered fuel (SRF) in a pulverized coal-fired power plant were sampled and characterized in this study. The particles from dedicated coal combustion and co-combustion both showed an ultrafine mode centered at approximately 0.1 μm. Compared with coal combustion, co-combustion of coal and SRF increased the formation of submicron particles, especially ultrafine particles below 0.2 μm. The morphology of the particles indicated that supermicron particles were primarily formed by the melting of minerals. The ultrafine particles were generated through nucleation and coagulation of vaporized inorganic species, while for the particles in between supermicron and ultrafine particles, condensation of vaporized species or aggregation of nucleates on the existing spherical submicron particles appear to be an important formation mechanism. The elemental composition of the particles from coal combustion showed that S and Ca were significantly enriched in ultrafine particles and P was also enriched considerably. However, compared with supermicron particles, the contents of Al, Si and K were depleted in ultrafine particles. The observed high volatility of Ca was likely related with the high combustion temperature and relative low oxygen condition in the boiler which may promote vaporization of Ca during char oxidation. The discrepancies on the observed volatilities of Ca and alkalis between some laboratory experiments and full-scale measurements were discussed. The composition of the fine particles from co-combustion was generally similar to those from coal combustion. The ultrafine particles from co-combustion were of slightly higher Ca, P, and K contents, and lower S content.