The large overpotentials during oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are still big challenges for the non-aqueous lithium-oxygen batteries. In this paper, CeO2 nanoparticles on N-doped reduced graphene oxide (CeO2@N-RGO) are in-situ synthesized through a one-step hydrothermal process as binder-free cathode catalyst. The battery with CeO2@N-RGO cathode delivers a capacity of 11,900mAhg−1 at current density of 400mAg−1, and can cycle up to 40 times without obvious degradation at the capacity limitation of 1000mAhg−1. The performance enhancement of the battery can be attributed to the synergetic effect of N-RGO and CeO2 nanoparyicles anchoring the formation of Li2O2. The study confirms that CeO2@N-RGO can be a potential excellent cathode catalyst for ORR and OER for rechargeable lithium-oxygen batteries.