Li-rich layered oxide Li[Li0.2Mn0.54Ni0.13Co0.13]O2 is synthesized by combustion reaction using alcohol as both solvent and fuel. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that the oxide synthesized at 800 °C exhibits perfect crystallinity and lattice ordering, and has particle sizes of 50–150 nm. The layered oxide delivers an initial discharge capacity of 290.1 mAh g−1 at a current density of 20 mA g−1 after activation, and exhibits improved rate capability with high discharge capacities of 238.6 and 165.0 mAh g−1 at current densities of 200 and 2000 mA g−1 in the voltage range of 2.0–4.8 V, respectively. Low Li-ion diffusion coefficient of 1.07 × 10−14−1.01 × 10−16 cm2 s−1 is calculated by galvanostatic intermittent titration technique (GITT) during the initial discharge process, indicating that the improved rate capability is mainly attributed to the small particle sizes of the Li-rich oxide.