Spinel-embedded lithium-rich oxides are synthesized and their structural phases are analyzed. The type of spinel Li M 0.5Mn1.5O4 ( M = Ni, Co, Mn) embedded is varied by controlling the spinel composition and content. Of the various composites fabricated with different spinel phases, the LiCo0.5Mn1.5O4-embedded over-lithiated layered oxide (OLO) shows the best electrochemical performance as a cathode because of the absence of a parasitic phase and its high structural stability. The formation energy of the LiCo0.5Mn1.5O4-embedded oxide is determined through first-principles calculations and is found to be lower than that of the pristine oxide as well as other spinel-phase-embedded oxides. It is also observed that use of OLO with optimal embedded spinel LiCo0.5Mn1.5O4 in a cylindrical 18650-type cell results in improvement in the full-cell electrochemical performance.