The effectiveness of electrolyte additives in fluorinated electrolytes containing 1 M LiPF6/fluoroethylene carbonate:bis (2,2,2-trifluoroethyl) carbonate (1:1 w:w) were studied in high voltage Li(Ni0.4Mn0.4Co0.2)O2/graphite pouch cells tested to 4.5 V. The results showed that fluorinated electrolytes containing prop-1-ene-1,3-sultone alone or in combination with other additives exhibited significant improvements in terms of coulombic efficiency and charge endpoint capacity slippage during UHPC cycling, voltage drop during storage, as well as capacity retention during long-term cycling compared with state-of-the-art ethylene carbonate-based (ethylene carbonate: ethylmethyl carbonate 3:7) or sulfolane-based electrolytes (sulfolane: ethylmethyl carbonate 3:7) with some promising additive blends. These results indicate that fluorinated electrolytes offer an interesting alternative for high voltage Li-ion batteries.