Ethyl-(2,2,2-trifluoroethyl) carbonate (ETFEC) is investigated as a solvent component in high-voltage electrolytes for LiNi0.5Mn1.5O4 (LNMO). Our results show that the self-discharge behavior and the high temperature cycle performance can be significantly improved by the addition of 10% ETFEC into the normal carbonate electrolytes, e.g., the capacity retention improved from 65.3% to 77.1% after 200 cycles at 60 °C. The main reason can be ascribed to the high stability of ETFEC which prevents large oxidation of the electrolyte on the cathode surface. In addition, we also explore the feasibility of electrolytes using single fluoriated-solvents with and without additives. Our results show that the cycle performance of LNMO material can be greatly improved in 1 M LiPF6 + pure ETFEC-solvent system with 2 wt% ethylene carbonate (EC) or ethylene sulfate (DTD). The capacity retention of the LNMO materials is 93% after 300 cycles, even better than that of carbonate-based electrolytes. It is shown that the additives are oxidized on the surface of LNMO particles and contribute to the formation of cathode/electrolyte interphase (CEI) films. This composite CEI film plays a crucial role in suppressing the serious decomposition of the electrolyte at high voltage.