Silica fume is a by-product of induction arc furnaces and has long been used as a mineral admixture to produce high-strength, high-performance concrete. Due to the pozzolanic reaction between calcium hydroxide and silica fume, compared with that of Portland cement, the hydration of concrete containing silica fume is much more complex. In this paper, by considering the production of calcium hydroxide in cement hydration and its consumption in the pozzolanic reaction, a numerical model is proposed to simulate the hydration of concrete containing silica fume. The heat evolution rate of silica fume concrete is determined from the contribution of cement hydration and the pozzolanic reaction. Furthermore, the temperature distribution and temperature history in hardening blended concrete are evaluated based on the degree of hydration of the cement and the mineral admixtures. The proposed model is verified through experimental data on concrete with different water-to-cement ratios and mineral admixture substitution ratios.