The　present　study　demonstrates　that　the　use　of　alkyl　3,3,3-trifluoropropanoate,　including　methyl　3,3,3-trifluoropropanoate　(TFPM)　and　ethyl　3,3,3-trifluoropropanoate　(TFPE),　as　new　electrolyte　additive　can　dramatically　enhance　the　high-voltage　performance　of　LiNi1/3Co1/3Mn1/3O2/graphite　lithium-ion　batteries　(3.0-4.6　V,　vs　Li/Li+).　The　capacity　retention　was　significantly　increased　from　45.6%　to　75.4%　after　100　charge-discharge　cycles　due　to　the　addition　of　0.2　wt　%　TFPM　in　the　electrolyte,　and　significantly　increased　from　45.6%　to　76.1%　after　100　charge-discharge　cycles　due　to　the　addition　of　0.5　wt　%　TFPE　in　the　electrolyte,　verifying　their　suitability　in　this　application.　Electrochemical　impedance　spectroscopy,　X-ray　diffraction,　Fourier　transform　infrared　spectroscopy,　scanning　electron　microscopy,　and　X-ray　photoelectron　spectroscopy　were　employed　to　study　the　effect　of　TFPM　and　TFPE　on　cell　performance.　The　data　indicates　that　the　improved　cycling　activity　can　be　ascribed　to　the　participation　of　TFPM　or　TFPE　in　the　formation　of　a　thinner　cathode/electrolyte　interfacial　film,　thereby　enhancing　the　cell　cycling　performance　owing　to　a　reduced　interfacial　resistance　at　high　voltage.　©　2017　American　Chemical　Society.