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The effect of grain size of CaCO3 and SiO2 on the formation of C3S under various conditions, such as rapid heating rate(800 ℃/min), normal heating rate(30 ℃/min) and in the presence or absence of ZnO,was studied. The results show that the decomposition temperature of CaCO3, the temperature of appearance of liquid phase and the f-CaO content descend when the grain size of CaCO3 and SiO2 becomes smaller, which attributes to the reactive activity enhancement of powders due to the decrease of the particle size. When the grain size of CaCO3 and SiO2 is below 1 μm, the rate of the formation of C3S is greatly raised. A rapid sintaring rate and the presence of ZnO have an important effect on the formation of C3S and can lower the temperature of the formation of C3S by about 50 ℃.