C14TAB-assisted cerium oxide (CeO2) mesocrystals have been synthesized via wet chemical route. XRD, SEM, AFM, EDS, FTIR, Raman, UV–vis and PL spectroscopy were employed to characterize the crystal phase, morphology, chemical composition and optical properties of the CeO2 mesocrystals. The experimental results showed that the product owned mesocrystal structure with self-assembly cubic architecture in the presence of C14TAB as a template. The growth mechanism of CeO2 mesocrystals has been predicted to explain the formation of CeO2 mesocrystals. CeO2 mesocrystals exhibit a very strong violet/blue emission centered at 421 nm and a weak green luminescence emission at around 524 nm. © 2012, The Author(s).