The application of newly electrified microwave heating to traditional processes of vapor-liquid mass transfer has given rise to many emerging process intensification technologies, such as microwave-induced evaporation separation and microwave-induced reactive (flash) distillation. Many researchers are eager to find suitable application scenarios for microwave technology by deeply understanding the role of microwaves in the separation process of vapor-liquid mass transfer. In this paper, we summarize the role of microwaves in the above processes from prespectives of the driving energy and microwave special effects, and briefly outline the bottlenecks in the current development to point out the research direction for subsequent fundamental investigations and industrial applications.