This review highlights the key importance of the selective exposure of crystal facets in nanostructured ceria and their effect on the formation of lattice oxygen vacancies and their mobility. These factors, in addition to surface area and concentration of surface defects greatly affect the resulting catalytic oxidation activity of the nanostructured ceria materials. To illustrate these aspects, this paper reviews the structure–activity relationship of nanoceria for the oxidation of CO and a range of volatile organic compounds (VOCs) such as o-xylene, naphthalene and toluene. Further mechanistic understanding of the formation of ceria at the nanoscale as well as advanced characterisation techniques are required to be able to design effective tailored nanostructured catalysts.