Lithium cobalt oxide (LiCoO2, LCO) has been widely used in electronic markets due to its high energy density and wide voltage range applications. Recently, high-voltage (HV, >4.5 V) operation has been required to obey the requirements of high energy density and cycle life in several applications such as electric vehicles and energy storage. However, the HV operation causes structure instability due to the over de-lithiation of LCO, as well as decomposing common carbonate solvents, thereby incurring the decay of battery performance. Moreover, a distortion of the CoO6octahedra of LCO during de-lithiation induces a rehybridization of the Co 3d and O 2p orbitals. According to above reasons, decreasing the Co-O covalent bond promptly triggers high risks that significantly limit further use of LCO. In this research, an organic surface reinforcement by using bismaleimide–uracil (BU) that electrochemically forms a cathode electrolyte interphase (CEI) on LCO was explored. The results of electrochemical impedance spectroscopy and battery performance, such as the c-rate and cyclability tests, demonstrated that the modified CEI formed from BU significantly prevents the distortion of CoO6octahedra. X-ray photoelectronic spectroscopy and in situ XAS indicated less LiF formation and higher bond energy of Co-O improved. Finally, the differential scanning calorimetry showed the onset temperature of decomposition of LCO was extended from 245 to 270 °C at 100% state of charge, which is about a 25 °C extension. The exothermic heat of LCO decreased by approximately 30% for high-safety use. This research confirms that the BU is eligible for high voltage (>4.5 V) LCO and presents outstanding electrochemical properties and safety performances.