Cu-doped Li2O, synthesized by mechanochemical reactions between Li2O and CuO, is demonstrated as a cathode material for lithium-ion batteries. The X-ray diffraction and absorption analyses suggest that in the Cu-doped Li2O, Cu2+ ions are located at 48g sites less symmetrical than 8c sites for Li+ ions, distorting the arrangement of surrounding O2− ions slightly from tetrahedral to square-planar, while the Cu2+ ions are doped in an antifluorite-type Li2O. The Cu-doped Li2O cathode has a charge capacity of 360 mAh g−1 without an irreversible O2 gas evolution reaction and exhibits a reversible capacity of 300 mAh g−1. Cu K-edge XANES spectroscopy and quantitative analysis of peroxide species reveal that redox of copper ions, formation/neutralization of O 2p electron holes, and generation/annihilation of peroxide species take place during charge/discharge.