Abstract: Analysis of the Si and Al phases in coal gangue fuel and its ash is important for use of coal gangue ashes. A comprehensive study by theoretical and experimental analyses with differential thermal analysis, X-ray diffraction and Infrared Spectroscopy has been made in the present article to explore the diagram of the Si and Al phases in coal gangue fuel and its ashes. It is found that kaolinite and quartz are the main phases in coal gangue fuel. The ratio of moles Al2O3 to SiO2 (i.e., Al2O3 (mole) /SiO2 (mole)) is usually no more than 0.5 in most coal gangue fuel and its ashes. The kaolinit at about 984°C releases a large quantity of SiO2, which makes calcine coal gangue more active than coal gangue itself. The relationship between the ratio Al2O3 (mole)/SiO2(mole) and the components of coal gangue ash is analyzed, resulting in a formula to calculate the quantity of each phase. Applying the formula to the testing samples from an electric plant in north China supports the above conclusions.