Lithium ion conducting membranes are barely studied, although they are essentially indispensable for building Li-air batteries composed of aqueous and non-aqueous electrolytes for long-term operation. Lithium phosphorous oxynitride (LiPON) thin films were deposited by RF-sputtering technique on B2O3-added lithium aluminum germanium phosphate (B-LAGP). Compact thin amorphous LiPON layer could act as a protective interlayer for B-LAGP by separating it from Li metal electrode and mitigate the reaction between them. Large electrochemical stability window (0–5V) of LiPON/B-LAGP solid electrolyte shows promising feasibility for applications in all lithium based batteries. The aprotic Li-O2 cell with protected lithium electrode configuration employing LiPON/B-LAGP solid electrolyte has exhibited reasonable cycling stability with long-life of 52 cycles at a limited capacity of 1000mAhg−1.