Analyses for concentration, surface phenomena, and crystal structure were performed to identify the causes of clinker formation in three type of pulverized coal fired boilers. Some clinkers had partially molten surface and more CaO and $Fe_2O_3$ as compared with fly ash, and the major crystalline phases identified in the clinker were mullite and quartz. Clinkers were formed in high temperature zone of the boiler according to the identification of mullite by XRD. Free $SiO_2$ in sand combined with K, Na and Ca in limestone served as a fluxing agent to form clinkers in a circulating bed boiler.