We developed a simple electrochemical process for the large-scale fabrication of single crystalline CeO2 octahedrons and nanospheres from DMSO aqueous solution. The octahedrons with some structural defects have a size ranging from 200 to 300 nm. Moreover, highly crystalline CeO2 nanospheres were also obtained via this electrochemical process based on the oriented attachment mechanism. The absorption edge of octahedrons and spheres shows a red-shift, and that of the octahedrons was near the visible region.