Solvent exchange method is widely used in the drying and hydration termination of cement-based materials. This review represented the influence of solvent exchange on the microstructure of cement paste. The selection principle of exchange parameters (i.e., sample size, liquid/solid ratio, exchange time and removal method) was described. The physical and chemical reactions between common exchange solvents (i.e., isopropanol, acetone, methanol, and ethanol) and cement hydration products (i.e., calcium hydroxide, calcium silicate hydrate and ettringite) were discussed. The pore structure parameters (i.e., porosity and pore size distribution) of cement-based materials were analyzed under the influence of exchange parameters and solvents. In addition, the existing problems and research prospects of the solvent exchange method were also given.