This experimental study investigated the trend of structure and dielectric properties during microwave freeze-drying process banana chips. The mass of banana samples was 160 g, the microwave power set as 2 W g−1 and the highest drying temperature set as 55 °C. The whole drying process can be finished within 6 h. A network analyser and light microscope were used to determine the dielectric properties and structure. The dielectric properties, ε′ (from 20.80 to 1.20) and ε′′ (from 7.74 to 0.15), and the size of cell get smaller as the drying process continues, especially during the 3–4 h drying, which is the end of primary drying stage and the beginning of secondary drying stage. The trend of dielectric properties and microstructure of samples during drying can be an exact indication of drying stage of MFD.