Particulate matter (PM) emission from the combustion of solid fuels potentially poses a severe threat to the environment. In this article, a novel approach was developed to examine the properties of individual particles in PM. With this method, PM emitted from combustion was first size-segregated. Subsequently, each size was characterized by computer-controlled scanning electron microscopy (CCSEM) for both bulk property and single particle analysis. Combustion of bituminous coal, dried sewage sludge (DSS) and their mixture were conducted at 1200°C in a laboratory-scale drop tube furnace. Three individual sizes smaller than 2.5 μm were investigated. The results indicate that a prior size-segregation can greatly minimize the particle size contrast and phase contrast on the backscattered images during CCSEM analysis. Consequently, high accuracy can be achieved for quantifying the sub-micron particles and their inherent volatile metals. Regarding the PM properties as attained, concentrations of volatile metals including Na, K, and Zn have a negative relationship with particle size; they are enriched in the smallest particles around 0.11 μm as studied here. Strong interactions can occur during the cofiring of coal and DSS, leading to the distinct properties of PM emitted from cofiring. The method developed here and results attained from it are helpful for management of the risks relating to PM emission during coal-fired boilers. © 2009 American Institute of Chemical Engineers AIChE J, 2009