The lithium-rich layered cathode material Li[Li0.2Mn0.54Ni0.13Co0.13]O2 with high capacity and excellent cycling stability, is successfully synthesized through a facile organic co-precipitation route. The as-obtained material exhibits a well-crystallization and uniform size distribution, above which have been characterized and observed by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Moreover, FT-IR spectra proves that the addition of metal ions Mn+ induces a red-shift of the bond of C–N groups of the 8-hydroxyquinoline, which is used as the precipitant in this work, and most probably due to the strong complexation effect of metal ions Mn+ with N and O atoms of 8-hydroxyquinoline, and simultaneously the co-precipitation process occurred. The electrochemical results reveal that the cathode material derived from this novel organic co-precipitation route exhibits improved electrochemical performance, of which could provide an initial discharge capacity of 287.2 mAhg−1at 0.2C within a potential range of 2.0–4.8 V at room temperature, even at high C-rate of 2C, this material could also deliver a capacity of 212.1 mAh g−1 with 97.7% capacity retention after 100 cycles. Therefore, it is proposed that this organic co-precipitation might be a high-efficiency strategy to synthesize alternative electrode materials with improved performance.