Li-rich layered composite Li[Li0.2Ni0.2Mn0.6]O2 is prepared by a novel approach in which carbon felt acts as a carrier for synthesis reaction. The as-prepared material is characterized by SEM, ICP and XRD, its electrochemical performance is also examined with galvanostatic charge/discharge and CV measurements. It is showed that the facile process controls effectively the particle growth (in size around 100–200 nm) of the composite and its chemical composition. The as-prepared material shows a high initial discharge capacity about 288 mAh g−1 when charged to 4.8 V, and a retained value of 246.8 mAh g−1 in the 40th cycle. The crystalline structure of the composite is simulated further by Material Studio. It is revealed that the composite has a compatible layer structure merged by Li2MnO3 and LiNi0.5Mn0.5O2, which makes substantial contribution to the cycleability of the electrode. In addition, the lithiation/delithiaion properties including charge transfer resistance and lithium ion diffusion coefficient are studied with electrochemical impedance spectra.