A novel electrolyte additive, 1,1′-sulfonyldiimidazole (SDM), is firstly reported to improve the cycling performance of LiNi0.5Mn1.5O4 at high voltage and elevated temperature (55 °C). Linear sweep voltammetry (LSV), initial differential capacity vs. voltage, and computation results indicate that SDM is oxidized at a lower potential than the solvents of the electrolyte. Coulombic efficiency and capacity retention of a Li/LiNi0.5Mn1.5O4 cell can be significantly enhanced in the presence of SDM, and moreover cells with SDM deliver lower impedance after 100 cycles at elevated temperature. To better understand the functional mechanism of the enhanced performance with incorporation of SDM in the electrolyte, ex-situ analytical techniques, including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and inductively coupled plasma mass spectrometry (ICP-MS) are employed to gain insight into the reaction mechanism of SDM on the LiNi0.5Mn1.5O4 electrode at high voltage and elevated temperature (55 °C). Surface analysis reveals that the improved electrochemical performance of the cells can be ascribed to the highly stable surface layer generated by SDM, which thus mitigates the detrimental decomposition of the electrolyte occurring and stabilizes the interphase of spinel LiNi0.5Mn1.5O4 cathode while cycling at high voltage and elevated temperature.