We investigated the relation between the cycle performance and crystal structural change during the charge–discharge process of LiMn 1.5 Ni 0.5 O 4 as a 5 V class cathode active material, which was prepared by changing the calcination temperature using the sol–gel method. The lithium content of Li 1−x Mn 1.5 Ni 0.5 O 4 (x=0.5, 0.7, 1.0) was controlled by electrochemical lithium extraction. The crystal structure was determined by Rietveld analysis using powder neutron diffraction. As a result, all samples consisted of three phases (space group: P4 3 32) of different lattice constants and Ni valences. The main phase, which has the maximum percentage, was shifted to a phase with a lower lattice constant with the decreasing lithium content, and then finally Li 1−x Mn 1.5 Ni 0.5 O 4 (x=1.0) was almost oxidized to Ni 4+ by a charging process. Furthermore, LiMn 1.5 Ni 0.5 O 4, , by changing the synthesis temperature, was different for a few oxidation processes; the structure of the phase at Ni 3+ was not stable based on the distortion of each phase and the Madelung energy. It was suggested that these factors should provide an effective cycle performance.