{100} planes of CeO 2 are unstable polar surfaces and important to enhance the oxygen storage capacity. However, a convenient method is still needed for the synthesis of ceria nanocubes which expose six {100} facets. Here, a new and facile synthesis strategy has been developed to synthesize single-crystalline nanocubes of CeO 2 . According to transmission electron microscopy, these nanocubes are enclosed by six {100} facets. It is proved that in the synthesis process, the acetate radical ions would adsorb on the positive charged Ce(OH) 3 formed from the reaction of Ce 3+ and ammonia, then partially inhibit the redox between Ce(OH) 3 and NO 3 − and protect the {100} facets during crystal growth. Meanwhile, the Ce 4+ ions would act as crystal seeds to facilitate the formation of single crystals. Both of the addition of Ce 4+ ions and CH 3 COO − ions are necessary for the synthesis of monocrystal ceria nanocubes. Throughout the synthesis process, it is moderate reaction conditions that the pressure is atmospheric pressure and temperature is no higher than 80 °C.