Rod-like hierarchical nano/micro structured lithium rich materials (RH-LNMO), Li1.2Ni0.2Mn0.6O2, have been synthesized using a facile hydrothermal method. The as-prepared samples are characterized by X-ray diffraction (XRD), filed emission scanning electron microscopy (FESEM) and transmission electron microscope (TEM). The rod-like hierarchical structures (1–3μm in width and 3–10μm in length) are assembled by nanoparticles with average sizes of 20–150nm. Electrochemical data demonstrates that lithium cells using this lithium rich material as the cathode exhibit excellent performances. This material retains a high discharge capacity of 212.5mAhg−1 (97% of the first discharge capacity) after 30 cycles at 1C-rate, and it yields an initial discharge capacity of 198mAhg−1 at 2C-rate. The superior performance is attributed to the merits of the hierarchical nano/micro structures.