The cycling performance of graphite/LiNi0.5Co0.2Mn0.3O2 battery in the electrolyte with different content (0, 0.5, 1.0, 2.0 wt.%) 1-propylphosphonic acid cyclic anhydride (PACA) is studied in this work. When 0.5 wt.% PACA additive is incorporated into the blank electrolyte, the capacity retention of graphite/LiNi0.5Co0.2Mn0.3O2 battery at high voltage after 100 cycles is increased from 79.12% to 91.84%. Electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) results reveal the mechanism that the surface film derived from PACA can decrease the surface film impedance of the cell (from 40.63 to 16.57 Ω), stabilize the structure of cathode material. Moreover, the investigation of PACA on the cycling performance of graphite electrode demonstrates that PACA function on LiNi0.5Co0.2Mn0.3O2 instead of graphite.