The understanding of factors influencing the performance of catalysts in the air cathode of a rechargeable lithium-oxygen battery, including overpotentials for oxygen reduction/evolution and discharge capacity, is essential for exploration of its ultimate application. This report describes new findings of an investigation of PdCu nanoalloys as cathode catalysts. Alloying Pd with oxophilic base metals such as Cu leads to reduction of the overpotentials and increase of the discharge capacity. The nanoalloy structures depend on the bimetallic composition, with an atomic ratio near 50:50 featuring mixed bcc and fcc structures. The discharge potential exhibits a maximum while the charge potential display a minimum in the range of 20-50% Cu, closer to 25% Cu, both of which correspond to a maximum reduction of the discharge charge overpotentials. The discharge capacity displays a gradual increase with Cu%. This type of catalytic synergy is believed to be associated with a combination of ensemble and ligand effects. In particular, the activation of oxygen on Pd sites and oxygen oxophilicity at the alloyed Cu sites in the catalyst may have played an important role in effectively activating oxygen and maneuvering surface superoxide/peroxide species. These findings have implications for the design of multifunctional cathode catalysts in rechargeable lithium-oxygen batteries. (C) 2016 Published by Elsevier B.V.