A novel epitaxial thin-film electrode for lithium batteries, with a composition of Li0.92Co0.65Mn1.35O4 and a cubic spinel structure, is fabricated on a SrTiO3(111) single-crystal substrate. Fabrication is carried out by layer-by-layer pulsed laser deposition of LiCoO2 with a layered rock-salt structure and LiMn2O4 with a spinel structure. The electrode is found to exhibit unique disordering of the lithium (8a) and transition-metal (16d) sites, leading to a higher rate capability and cycle retention ratio than those for a thin-film electrode with the same composition prepared by a conventional single-step deposition process. The proposed layer-by-layer deposition method allows an expanded range of compositional and structural variations for lithium battery electrode materials.