The chemistry, mineralogy, morphology, and particle size distribution were investigated in fly ashes from the burning of Datong (ShanXi, China) bituminous coal and the cofiring of Mideast high-sulfur petroleum coke ( PC) with 30: 70 (cal %) and 50: 50 ( cal %) blends of Datong bituminous coal in two commercial CFBC boilers. With the exception of CaO, the amounts of major oxides in the fly ashes from cofiring PC and coal were close to those of the common coal fly ashes. The PC-coal fly ashes were enriched in Ni, V, and Mo, implying these trace elements were mainly derived from PC. Ni and V, along with several other elements, such as Cr, Cu, Se, Pb, U, Th, and possibly As and Cd, increased in content with a decrease in temperature of the electrostatic precipitator ( ESP). The results of chemistry, mineralogy, and morphology studies suggested that the desulfurization rate of the CFBC boilers at current conditions was low, and the PC tends to coarsen the fly ash particles and increase the loss on ignition (LOI) values, making these fly ashes unsuitable for use as a cement additive or a mineral admixture in concrete. Further studies on the combustion status of the CFBC boilers are needed if we want to be able to increase the desulfurization rate and produce high-quality fly ashes for broader and full utilization.