Single-crystal Ni-rich layered oxide materials LiNi1−x−yCoxMnyO2 (NCM, 1 – x − y ≥ 0.6) are emerging as promising cathode materials that do not show intergranular cracks as a result of the lack of grain boundaries and anisotropy of the bulk structure, enabling extended cyclability in lithium-ion batteries (LIBs) operating at high voltage. However, SC-NCM materials still suffer from capacity fading upon extended cycling. This degradation of capacity can be attributed to a reconstruction of the surface. A phase transformation from layered structures to disordered spinel/rock-salt structures was found to be responsible for impedance growth and capacity loss. Film-forming additives are a straightforward approach for the mitigation of surface reconstruction via the formation of a robust protection layer at the cathode’s surface. In this work, we investigate various additives on the electrochemical performance of single-crystal LiNi0.83Co0.11Mn0.06O2 (SC-NCM83). The results demonstrate that the use of 1% lithium difluoroxalate borate (LiDFOB) and 1% lithium difluorophosphate (LiPO2F2) additives substantially enhanced the cycling performance (with a capacity retention of 93.6% after 150 cycles) and rate capability in comparison to the baseline electrolyte (72.7%) as well as electrolytes using 1% LiDFOB (90.5%) or 1% LiPO2F2 (88.3%) individually. The superior cycling stability of the cell using the combination of both additives was attributed to the formation of a conformal cathode/electrolyte interface (CEI) layer, resulting in a stabilized bulk structure and decreased impedance upon long-term cycling, as evidenced via a combination of state-of-the-art analytical techniques.