A novel method, the program process of microwave irradiation (PPMI), which commendably integrates good qualities of microwave irradiation and a programmed heating process, is presented to synthesize high-quality CdTe nanocrystals in aqueous solution. Microwave irradiation, which acts as the heating mode of PPMI, is highly favorable for a narrow size distribution and low concentration of surface defects of nanocrystals. On the other hand, two correlative processes ( the first process and the second process) are utilized in PPMI to actualize the programmed heating process, which is an effective strategy to improve the quality of nanocrystals. Thus, a series (diameters similar to 2-4 nm) of highly luminescent (PLQY similar to 30-68%) CdTe nanocrystals were rapidly prepared ( reaction time similar to 1-30 min) in aqueous phase through PPMI.