Compared with the advanced anode, the energy density of LIBs is more largely determined by discharge capacity and voltage of the cathode. [3][4][5] Lithium and manganese rich nickel cobalt manganese oxide (LMRNCM), xLi 2 MnO 3 •(1-x)LiTMO 2 (TM (transition metal) = Mn, Ni, Co), has been considered as an attractive next-generation cathode candidate owing to its high energy density (≈1000 Wh kg −1 ) and low cost. [6] According to the charge compensation mechanism and the energy level theory, when the Li + extraction voltage is lower than 4.4 V, the TM ions of high electron energy level is mainly oxidized to maintain electrical neutrality. [7,8] When the voltage is higher than 4.4 V, the electronic energy level of TM 4+ →TM n+ (n > 4) is lower than that of O 2− →O m− (0 ≤ m < 2), [9,10] and the electrical neutrality is maintained by the oxidation of lattice oxygen. On the one hand, lattice oxygen redox reaction provides higher specific capacity, [11,12] which is a key factor that determines high energy density. On the other hand, the unstable high-valence lattice oxygen accelerates the degradation of the LMRNCM layered structure. [13] Specifically, high-valence oxygen is unstable in the crystal lattice, and is easily released with Li + in the form of Li 2 O. [14] The absence of lattice oxygen in the octahedron causes unstable Lithium and manganese rich nickel cobalt manganese oxide (LMRNCM), as an attractive high energy density cathode for advanced lithium-ion batteries (LIBs), suffers from inevitable lattice oxygen release, irreversible transition metal (TM) ion migration, and interface side reactions at high charge cut-off voltage. Herein, a facile and efficient surface strategy is proposed to stabilize the layered structure by regulating the chemical bond interaction between the polyacrylonitrile (PAN) binder and the LMRNCM particles. Due to the high retention of discharge specific capacity and average discharge voltage, the energy density retention of the PAN-modified LMRNCM sample is up to 80.12% after 300 cycles at 100 mA g −1 current density, and the initial Coulombic efficiency and rate capacity are also improved simultaneously. Experimental and density functional theory evidence demonstrates that the exceptional performance is caused by the coordination bond interaction between the carbon-nitrogen-triple-bond of PAN and the TM ion in the unstable transition metal oxygen octahedron. The interaction suppresses the irreversible migration of TM ions by increasing the energy barrier, and ensures that the PAN adheres to the LMRNCM particles tightly, which relieves electrolyte corrosion and enhances cohesiveness. This work exploits a modification strategy to stabilize the LMRNCM-layered structure for high-energy density LIB applications.