Layered Li0.7[M1/6Mn5/6]O2 (M=Li, Ni) was synthesized using a sol–gel method. P2-Na0.7[M1/6Mn5/6]O2 precursor was first synthesized by a sol–gel method, and then O2-Li0.7[M1/6Mn5/6]O2 was prepared by an ion exchange of Li for Na in P2-Na0.7[M1/6Mn5/6]O2 precursor. From charge/discharge curves, it was seen that Li0.7[Li1/6Mn5/6]O2 has two plateaus similar to those observed from a spinel structure, but Li0.7[Ni1/6Mn5/6]O2 holds a single plateau as observed from a typical layered structure. It was considered that Li0.7[Li1/6Mn5/6]O2 undergoes a phase transformation from layered to spinel structure during the charge/discharge cycle, but Li0.7[Ni1/6Mn5/6]O2 maintains O2-layered structure after the cycles. Li0.7[Ni1/6Mn5/6]O2 was higher in discharge capacity and retention rate than Li0.7[Li1/6Mn5/6]O2.