Amorphous lithium phosphorous oxynitride film was coated directly on pre-treated lithium metal as anode of lithium air battery by radio-frequency sputtering technique from a Li3PO4 target. The structure and composition of modified anode was analyzed before and after charge/discharge test in a lithium-air battery, which comprises 0.5M LiNO3/TEGDME as the electrolyte and super P carbon as cathode. Batteries were galvanostatically discharged by an Arbin BT-2000 battery tester between open current voltage and 2.15V vs. Li+/Li at various current regimes ranging from 0.1–0.4mA/cm2. Compared with fresh lithium, LIPON-coated anode exhibited better electrochemical performance. Good charging efficiency of 90% at a narrower voltage gap with high ionic conductivity of 9.4×10−5 S/cm was achieved through optimizing lithium pre-treated conditions, sputtering N2 flows and suitable solute for electrolyte.