Annular pressure has been recognized as one of the most challenging problems in the petroleum industry, posing a series of threats to wellbore integrity. Annular pressure caused by thermal expansion during the cement hydration process is rarely studied by researchers. In light of the hydration heat generation process, a kinetics model for cement hydration under different curing temperatures is demonstrated in this paper. Considering interactions between temperature and cement hydration, a transient temperature prediction model during well cementing is built. On the basis of these assumptions, the prediction model of annular pressure is established, considering the change in cement temperature and the change in annulus volume. Using the models illustrated in this paper, a series of numerical simulations are performed. The changing roles of transient cement hydration degree and temperature in wellbores are analyzed thoroughly. The annular pressure during well cementing shows a rapid increase and then a decrease, which is similar to that of the temperature. In addition, a sensitive analysis of annular pressure is conducted. The analysis shows that the annular pressure increases with the geothermal gradient, the cement hydration heat, and the wellbore diameter. Suggestions and conclusions can provide safety guidance for the management of annular pressure during well cementing.