Cement hydration is a complex chemical and physical reaction process, which directly determines the microstructure and macro-property of hardened cement paste. Since conventional experimental methods are in general time-consuming, laborious and expensive, computer simulation thus becomes popular in understanding the mechanism of cement hydration and microstructure development in recent years. In this review, existing hydration models were introduced, and their advantages and drawbacks were described. Recent work on the cement hydration simulation were summarized, in which the emphasis is on the hydration of non-spherical cement particles and nano-scale simulation of calcium silicate hydrate. Based on the practical application of relevant models, the effect of mineral admixtures on the hydration process and microstructure of cement paste was discussed. The properties of cement-based materials (i.e., agent transport, chloride diffusion and microcrack propagation) were represented as well.