Different crystal planes of CeO2 have a different number of broken bonds, surface energy and catalytic activities, so preparing the CeO2 with different exposed planes has attracted extensive attention. In recent years, the preparation of CeO2 nanocubes with {100} exposed plane has been a real hotspot of research because of its good catalytic performance. Based on the research about the alkali concentration, reaction temperature and reaction time, the formation mechanism of CeO2 nanocubes was explored. It is believed that the dissolution‐recrystallization process is accelerated in the condition of strong base, high temperature and high pressure. In other word, the Ostwald ripening process is strengthened, which is the decisive factor for the formation of CeO2 nanocubes.