The cathode/electrolyte interface stability is the key factor for the cyclic performance and the safety performance of lithium ion batteries. Suppression of consuming key elements in the electrode materials is essential in this concern. In this purpose, we investigate a facile strategy to solve interfacial issue for high-voltage lithium ion batteries by adding an oxidable fluorinated phosphate, Bis(2,2,2-trifluoroethyl) Phosphite (BTFEP), as a sacrificial additive in electrolyte. We demonstrate that BTFEP additive could be oxidized at slightly above 4.28V which is a relatively lower voltage than that of solvents, and the oxidative products facilitate in-situ forming a stable solid electrolyte interphase (SEI) film on the cathode surface. The results manifest the SEI film validly restrains the generation of HF and the interfacial side reaction between high-voltage charged LiNi0.5Mn1.5O4 (LNMO) and electrolyte, hence, the dissolution of Mn and Ni is effectively suppressed. Finally, the cyclic performance of LNMO after 200 cycles was remarkably improved from 68.4% in blank electrolyte to 95% in 1wt% BTFEP-adding electrolyte.