In order to investigate the effects of microwave curing on the microstructure of the interfacial transition zone of mortar prepared with a composite binder containing glass powder and to explain the mechanism of microwave curing on the improvement of compressive strength, in this study, the compressive strength of mortar under microwave curing was compared against mortar cured using (a) normal curing at 20 ± 1 °C with relative humidity (RH) > 90%; (b) steam curing at 40 °C for 10 h; and (c) steam curing at 80 °C for 4 h. The microstructure of the interfacial transition zone of mortar under the four curing regimes was analyzed by Scanning electron microscopy (SEM). The results showed that the improvement of the compressive strength of mortar under microwave curing can be attributed to the amelioration of the microstructure of the interfacial transition zone. The hydration degree of cement is accelerated by the thermal effect of microwave curing and Na+ partially dissolved from the fine glass powder to form more reticular calcium silicate hydrate, which connects the aggregate, calcium hydroxide, and non-hydrated cement and glass powder into a denser integral structure. In addition, a more stable triangular structure of calcium hydroxide contributes to the improvement of compressive strength.