The electrochemical performance and electrode reaction using Au–Pd nanoparticle (NP) supported mesoporous β-MnO2 as a cathode catalyst for rechargeable Lithium-Air (Li-Air) battery is reported here for the first time. In this study, Au–Pd NP-supported mesoporous β-MnO2 was successfully synthesized by hydrothermal process using a silica KIT-6 template. It has an initial discharge capacity of ca. 775 mAh g−1 with high reversible capacity at a current density of 0.13 mA cm−2. The Au–Pd NP-supported mesoporous β-MnO2 cathode catalyst, which enhances the kinetic of oxygen reduction and evolution reactions (ORR/OERs), thereby improves energy and coulombic efficiency of the Li-Air cell. Raman spectroscopy and ex-situ XRD results of the Au–Pd NP-supported mesoporous β-MnO2 air electrode suggest that the observed capacity comes from oxidation of Li+ to form Li2O2 during discharge to 2.0 V.