Nanocrystalline magnesium aluminate (MgAl2O4) powders were prepared by high-energy milling of the bulk material. Due to the ability of nuclear magnetic resonance (NMR) spectroscopy to discriminate between probe nuclei on inequivalent crystallographic sites, valuable insight into the mechanically induced evolution of a local cation disorder in MgAl2O4 can be obtained. It, thus, was revealed for the first time that the mechanical treatment of MgAl2O4 tends to randomize ions over the cation spinel sublattices. Quantitative microstructural information on the nonequilibrium cation distribution provided by Al-27 MAS-NMR is complemented by XRD and TEM investigations revealing the nanoscale nature of the milled material. The cation inversion parameter of the nanosized MgAl2O4 is compared with that of the bulk material at non-ambient conditions. (c) 2006 Elsevier B.V. All rights reserved.