We investigated the effectiveness of using methylboronic acid MIDA ester (ADM) as an additive in an electrolyte to enhance the overall electrochemical and material properties of an LNCAO (LiNi0.8Co0.15Al0.05O2) cathode. The cyclic stability of the cathode material measured at 40 °C (@ 0.2 C) showed an enhanced capacity of 144.28 mAh g−1(@ 100 cycles), a capacity retention of 80%, and a high coulombic efficiency (99.5%), in contrast to these same properties without the electrolyte additive (37.5 mAh g−1, ~ 20%, and 90.4%), thus confirming the effectiveness of the additive. A Fourier transform infrared spectroscopy (FTIR) analysis distinctly showed that the ADM additive suppressed the EC-Li+ion coordination (1197 cm−1and 728 cm−1) in the electrolyte, thereby improving the cyclic performance of the LNCAO cathode. The cathode after 100 charge/discharge cycles revealed that the ADM-containing system exhibited better surface stability of the grains in the LNCAO cathode, whereas distinct cracks were observed in the system without the ADM in the electrolyte. A transmission electron microscopy (TEM) analysis revealed the presence of a thin, uniform and dense cathode electrolyte interface (CEI) film on the surface of LNCAO cathode. An operando synchrotron X-ray diffraction (XRD) test identified the high structural reversibility of the LNCAO cathode with a CEI layer formed by the ADM, which effectively maintained the structural stability of the layered material. The additive effectively inhibited the decomposition of electrolyte compositions, as confirmed by X-ray photoelectron spectroscopy (XPS).