Cobalt and chromium substituted lithium-excessmanganese oxides, Li[Li0.2CoxCr0.4-xMn(0.4)]O-2 (x = 0, 0.2, and 0.4), are synthesized by a simple combustion method. Crystal structures of the samples are examined by an X-ray diffraction (XRD) method. The samples crystallize into a rhombohedral layered phase with in-plane cation ordering between lithium and transition metal ions. Li[Li0.2Co0.2Cr0.2Mn0.4]O-2 can deliver more than 200 mAh g(-1) of discharge capacity above 3.0 V vs. Li at a rate of 10 mA g(-1). Discharge capacity further increases to 300 mAh g(-1) when the Li cell is discharged to 1.5 V with appearance of a voltage plateau at 1.7 V. A combined study of synchrotron XRD and X-ray absorption spectroscopy (XAS) reveals that originally trivalent chromium ions are oxidized to hexavalent state, resulting in the migration of chromium ions into face-shared tetrahedral sites in lithium layers. Although a part of hexavalent chromium ions are immobilized at the tetrahedral sites, the reduction process to 1.5 V allows the chromium ions to migrate to octahedral sites associated with the reduction process to trivalent state. The chromium substitution has a beneficial effect on stabilization of oxide ion framework structures of the lithium-excess manganese system by suppressing oxygen loss upon charge to a high voltage region, leading to good cyclability as electrode materials. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.045301jes] All rights reserved.