Ni-rich layered cathodes are regarded as a potential candidate for high energy-density lithium-ion batteries, but their high sensitivity to air during storage and poor thermal stability are a vital challenge for large-scale applications. In this paper, an effective solid-solution strategy was proposed to improve the surface and structural stability of Ni-rich layered cathodes by introducing Li2MnO3. The structural analysis results indicate that the formation of Li2CO3 inert layers on Ni-rich layered cathodes during storage in air is responsible for the increased electrode interfacial impedance, thereby resulting in the severe deterioration of electrochemical performance. The introduction of Li2MnO3 can reduce the surface reactivity of Ni-rich cathode materials, playing a certain suppression effect on the formation of surface Li2CO3 layer and the deterioration of electrochemical performances. Additionally, the thermal analysis results show that the heat release of Ni-rich cathodes strongly depends on the charge of states, and Li2MnO3 can suppress oxygen release and significantly improves the thermal stability of Ni-rich layered cathodes. This work provide a method to improve the storage performance and thermal stability of Ni-rich cathode materials.