The morphologies and exposed surfaces of ceria nanocrystals are important factors in determining their performance. In order to establish a structure–property relationship for ceria nanomaterials, it is essential to have materials with well-defined morphologies and specific exposed facets. This is also crucial for acquiring high resolution ¹⁷O solid-state NMR spectra. In this study, we explore the synthesis conditions for preparing CeO₂ nanorods with exposed (111) facets. The effects of alkali concentration, hydrothermal temperature and time, cerium source and oxidation agent are investigated and optimal synthesis conditions are found. The resulting CeO₂ nanorods show very narrow ¹⁷O NMR peaks for the oxygen ions in the first, second and third layers, providing a foundation for future research on mechanisms involving ceria materials using ¹⁷O solid-state NMR spectroscopy.