p-Toluenesulfonyl isocyanate (PTSI) is introduced as electrolyte additive in a bid to enhance the electrochemical performances of LiNi0.5Co0.2Mn0.3O2 cathode materials under high voltage. A less resistive and stable film on the cathode surface derived from PTSI oxidation which taken place prior to the carbonate solvents is formed. As a result, the discharge capacity retention of Li/LiNi0.5Co0.2Mn0.3O2 cell is elevated from 71.4% to 86.2% after 100 cycles at room temperature, and from 32.3% to 54.5% after 100 cycles at 55 °C. In addition, the Li/LiNi0.5Co0.2Mn0.3O2 half cell with PTSI exhibits superior rate capability compared to that in baseline electrolyte. The improved performance is not only ascribed to the thin protective layer originated from PTSI decomposition which prevent the successive breakdown of the electrolyte on cathode surface, but it is also attributed to the SO group in PTSI serves as the weak base site to restrain the reactivity of PF5, resulting in the suppression of LiF formation and HF generation.