Developing an efficient cathode catalyst material is the most intrinsic requisite to acquire rechargeable Li-O-2 batteries with long cycling life and high rate capacity. Here, yolk-shell structured Cu2O spheres were facilely synthesized using a wet-chemistry method with the PEG-500 as the surfactant. As catalyst cathode materials, yolk-shell structured Cu2O spheres show a low discharge/charge potential platform of 1.28 V with current density of 500 mA g(-1). Compared with cubic-like Cu2O nanoparticles, yolk-shell structured Cu2O spheres have indicated a long and stable cycling life of 84 cycles with a high current density of 500 mA g(-1), and which may be benefited to the porous structure and the large specific surface area. The introduction of Cu2O provides an effective solution to the problem of low round-trip efficiency in the Li-O-2 battery.