Layered Li1.3Mn0.58Ni0.12Co0.11O2+δ, a solid solution of 0.53 Li2MnO3⋅0.47 LiMn0.4Ni0.3Co0.3O2, has been successfully synthesized by using an improved solvothermal strategy and used as the cathode material of a Li‐ion battery. The pure phase of the layered structure is characterized by using X‐ray diffraction and Raman spectroscopy. Electrochemical tests demonstrate that as‐synthesized layered Li1.3Mn0.58Ni0.12Co0.11O2+δ exhibits high discharge capacities of 349.4, 322.4, 304.6, and 291.7 mAh g−1 at 0.1, 0.2, 0.5, and 1 C rates, respectively. Such high reversible capacities could be ascribed to the enrichment of oxygen in the materials, which was evidenced clearly by a potential plateau below 3.0 V in the discharge process and originated form the electrochemical oxygen reduction.