In this work, we report a novel cathode composed of three-dimensional intersected graphene nanoribbons skeleton decorated with RuO2 catalyst, where graphene nanoribbons are obtained by unzipping multi-walled carbon nanotubes. The graphene nanoribbons framework exhibits a three-dimensional intersected structure and a large specific surface area, leading to a higher capacity than multi-walled carbon nanotubes. The RuO2 introduced via a facile dropping method enhances the oxygen evolution reaction kinetics and obviously reduces the charge overpotential. More importantly, the Li–O2 battery with RuO2 decorated graphene nanoribbons cathode presents an excellent cycling stability of 424cycles at a curtailed capacity of 1000 mAh g−1, which can be attributed to the synergistic effect between the intersected band-like graphene and highly effective RuO2 particles. The Li2O2 deposited on graphene nanoribbons shows a totally different surface morphology compared with that on multi-walled carbon nanotubes due to the different structures of carbon substrates. This work provides a promising design of highly efficient air electrodes for high-performance Li–O2 batteries.