Lithium-oxygen batteries with high theoretical energy densities have great potential. Recent studies have focused on different cathode architecture design to address poor cycling performance, while the impact of interface stability on cathode side has been barely reported. In this study, we introduce CoO mesoporous spheres into cathode, where the growth of crystalline discharge products (Li2O2) is directly observed on the CoO surface from aberration-corrected STEM. This CoO based cathode demonstrates more than 300 discharge/charge cycles with excessive lithium anode. Under deep discharge/charge, CoO cathode exhibited superior cycle performance than that of Co3O4 with similar nanostructure. This improved cycle performance can be ascribed to a more favorable adsorption configuration of Li2O2 intermediates (LiO2) on CoO surface, which is demonstrated through DFT calculation. The favorable adsorption of LiO2 plays an important role in the enhanced cycle performance, which reduced the contact of LiO2 to carbon materials and further alleviated the side reactions during charge process. This compatible interface design may provide an effective approach in protecting carbon-based cathodes in metal-oxygen batteries.