This paper reveals a novel Li-rich layered cathode material Li[Li0.1Ni0.45Mn0.45]O2 in situ coated with graphene-like carbon prepared by using liquid-polyacrylonitrile (LPAN) as the carbon source. The structure and electrochemical performance of graphene-like carbon coated Li[Li0.1Ni0.45Mn0.45]O2 are investigated systematically. The results demonstrate that the graphene-like carbon are in situ coated tightly on the surface of Li[Li0.1Ni0.45Mn0.45]O2 particles. The in-situ coating of graphene-like carbon significantly improves the electrochemical properties of cathode materials. The discharge capacity of cell made of 12wt% LPAN-coated Li[Li0.1Ni0.45Mn0.45]O2 can reach 210mAhg−1 and the capacity retention is close to 100% after 50 cycles at 0.1C. The cyclic voltammgram and electrochemical impedance spectra analyses further demonstrate that the improved electrochemical performance of LPAN-coated Li[Li0.1Ni0.45Mn0.45]O2 cathode materials is attributed to the graphene-like carbon in situ coating, which can protect the cathode directly contact with the electrolyte. Therefore, the Li-rich layered Li[Li0.1Ni0.45Mn0.45]O2 in situ coated with graphene-like carbon is a very good promise cathode material for advanced LIB with high capacity and good stability.