In order to overcome the capacity fading of LiCoO2/graphite Lithium-ion batteries (LIBs) cycled in the voltage range of 3.0–4.5 V (vs. Li/Li+), methylene methanedisulfonate (MMDS) is newly evaluated as an electrolyte additive. The linear sweep voltammetry (LSV) and cyclic voltammetry (CV) indicate that MMDS has a lower oxidation potential in the mixed solvents of ethylene carbonate (EC) and ethyl methyl carbonate (EMC), and participates in the formation process of the cathode electrolyte interface (CEI) film. With the addition of 0.5 wt.% MMDS into the electrolyte, the capacity retention of the LiCoO2/graphite cells cycled in 3.0–4.5 V is significantly increased from 32.0% to 69.6% after 150 cycles, and the rate capacity is also improved compared with the cells without MMDS additive in the electrolyte, showing the promising prospect in the electrolyte. In addition, the results of electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) demonstrate that the enhanced electrochemical performances of the cells can be ascribed to the modification of components of cathodes surface layer in the presence of MMDS, which resulting the suppression of the electrolyte oxidized decomposition and the improvement of CEI conductivity.