Carbothermal reduction using sucrose was applied to Fe- and/or Ti-substituted Li2MnO3 positive electrode materials to improve their poor initial cycle efficiency (<60%) of 2.0–4.8 V. The initial cycle efficiency was improved from 53% to 68% for Li1+x (Ti0.5Mn0.5)1−x O2, 63%–72% for Li1+x (Fe0.3Mn0.7)1−x O2, or 62%–78% for Li1+x (Fe0.2Ti0.2Mn0.6)1−x O2 by application of the carbothermal reduction process. All samples belong to 3.2 V class positive electrode material with high initial discharge capacity higher than 220 mAh g−1. The shape change of discharge curve with cycle progression was suppressed for all reduced samples. The compositional, transition metal valence state, and structural and powder property changes occurring before and after carbothermal reduction processing were examined to construct the material design concept of attractive Li2MnO3-based positive electrode candidates using only naturally abundant and cheap elements (Ti and Fe) as constituent metals.