Abstract. A series of cathode materials has been synthesized with the general formula LiMgNi0.5-Mn1.5O4 (=0.00, 0.05 and 0.10). These are promising cathode materials for lithium and Li-ion batteries due to the high voltage (4.7V vs. Li/Li+) and the high energy density (570Wh/kg). The cycling stability of these materials is strongly influenced by the method of synthesis and is particularly improved by a very low cooling rate. To study the effect of such slow cooling on the crystal structure, a detailed diffraction analysis was performed. Initial X-ray-diffraction (XRD) measurements revealed that the materials crystallize in the spinel structure, which is normally refined in the Fd m space group. Neutron-diffraction (ND) experiments, however, indicate space group P4332 and refinements of the ND and XRD patterns result in the site occupations: Li+ on 8c, Mg2+ and Ni2+ on 4b, Mn4+ on 12d and O2- on 24e and 8c. It was also found that, as a function of the Mg content, the cubic lattice constant increases from 8.1685 (=0.00) to 8.1733 (=0.10).