High-voltage operation of LiNixMnyCo1-x-yO2 (NMC) cathodes is gaining significant attention for advanced lithium-ion batteries (LIBs) with high energy density that can enable energy conversion and storage for mid- and large-scale applications. However, it is challenging to mitigate the detrimental effects of rapid capacity fading over short cycle durations because of severe continuous electrolyte decomposition and instability at the electrode surface, which are generally present in high cut-off voltage cycling. In this study, the unprecedented sulfate-based compound, [4,4-bi(1,3,2-dioxathiolane)] 2,2,2,2-tetraoxide (BDTT), is employed as a novel cathode stabilizing additive combined with vinylene carbonate, a well-known anode stabilizing additive, to enhance the electrochemical performance of a LiNi0.5Mn0.3Co0.2O2/graphite full cell. A synergistic effect of the dual cathode and anode stabilizer additive inclusion on the cycling performance results in high capacity and 86% of capacity retention for long operation (200 cycles). Prevention of IR drop and polarization in both charge and discharge cycles are achieved via dual additive combination. The results clearly indicate the importance of developing new additives and the potential of additive combination for improved high-voltage lithium-ion battery performance.