Through testing the amount of the free lime and the Loss ignition, the clinker formation rate, the reaction-rate constant (K) and the activation energy (Ea) were calculated according to the Gentling equation and Arrhenius equation. The effects of CaF2 on the formation kinetics of Portland cement clinker were investigated by analyzing the K and Ea. X-ray diffraction (XRD) and scanning electron Microscope (SEM) were used to characterize the phase composition and the morphology of the resulting samples. The results show that the silicate minerals formation is promoted when a proper amount of CaF2 is doped into the raw meal. The K increased from 0.7450 ×10-5s-1 to 7.1588 ×10-5s-1 and the Ea decreased from 386 kJ/mol to 122 kJ/mol when the amount of CaF2 increased from 0.0% to 2.0% in mass. However, the results were reversed at the amount of CaF2 exceeding 2%.