Lithium–chromium–manganese oxides, LiMn x Cr1−x O2 (0≤x≤0.6), were synthesized as solid solutions by simple calcination of emulsion-dried powder precursor. The product was well crystallized to an α-NaFeO2 structure (space group: R 3 ̄ m). By combination of Rietveld analysis of X-ray diffraction data and X-ray absorption near edge structure (XANES) techniques, the final product is considered to be [LiI]3a oct[Mn x IIICr1−x III]3b oct[O2]6c (0≤x≤0.6). The prepared oxides were electrochemically active, and capacity as cathode materials for lithium-ion battery was improved with increasing Mn substitution amount.