Ni-rich LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) is considered the most prominent cathode material to establish a practical high energy density of lithiumion batteries (LIBs) for future electric vehicles. The energy density of LIBs is greatly determined by the capacity of electrode materials and the operating voltage of the cells. To further improve the cycle lifespan of NCM811 batteries to meet the requirement of driving range for the electric vehicle market, it is vital to design a novel electrolyte additive that can enhance the stability of the cathode/ electrolyte interface at a wide range of voltage. Herein, a novel borate functionalized disiloxane compound, 1,1,1,3,3-pentamethyl-3-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl) disiloxane (PMBPDS), is synthesized as cathode electrolyte interphase (CEI) film-forming additive to improve the cycling performance of NCM811 batteries. Systematic studies reveal that PMBPDS can construct a stable CEI film on the NCM811 surface and efficiently scavenge hydrofluoric acid (HF). The PMBPDS-derived CEI prevents the dissolution of transmission metals in the NCM811 cathode and enhances the capacity retention of NCM811/graphite cells from 68.3 to 70.6% after 200 cycles at 1 C in the voltage window of 3−4.5 V. This work provides more understanding on designing the molecular structure of additive compounds for improving the electrochemical performance of LIBs. KEYWORDS: LiNi 0.8 Co 0.1 Mn 0.1 O 2 , borate functionalization, disiloxane, electrolyte additive, cycle life