Poly[bis-(ethoxyethoxyethoxy)phosphazene] (EEEP) with electro-oxidable of the P-O bond is prepared by a facile method and utilized as an electrolyte additive to enhance the cycling performance of LiCoO2 cathodes under high-voltage operations. We found that 5 wt.% EEEP made the blank electrolyte obviously reduce the flammability, as well as the capacity retention of Li/LiCoO2 half-cell assembling with the EEEPcontaining electrolyte is elevated to 89.9% from 51.2% after 100 cycles at a high cutoff voltage of 4.4V. The enhanced cycling performance of LiCoO2 cathode in the EEEP-containing electrolyte at a high potential should be ascribed to the formation of stable film on the cathode surface, resulting in suppression of the subsequent decomposition of electrolyte under high voltage working. The characterization from scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) indicates that EEEP can be electrochemically oxidized to form a robust and protective film on LiCoO2, and improve the interfacial stability of LiCoO2 cathode/electrolyte at high potentials. (C) 2017 Elsevier B.V. All rights reserved.