The rechargeable Li-air battery has a key role to play as a storage system for renewable energy and as the power system for electric vehicles. Effective cathode materials are required to improve its capacity, cycling ability and rate capability. In this work, an ionic conductive Li-Nafion® binder and Li-Nafion® membrane materials were fabricated and used to construct a novel rechargeable Li-O2/air and all-solid battery. The battery achieved a high capacity over 1000mA h (g solids)−1 with good rate capability and capacity retention were achieved. Insight into the improved performance has been explored with the aid of TEM, XRD, galvanostatic charge discharge test and impedance analysis.