AbstractNa‐O2 batteries are advantageous as the candidates of next‐generation electric vehicles due to their ultrahigh theoretical energy density and have attracted enormous attention recently. Tremendous efforts have been devoted to improve the Na‐O2 battery performance by designing advanced electrodes with various carbon‐based materials. Carbon materials used in Na‐O2 batteries not only function as the air electrode to provide active sites and accommodate discharge products but also as Na anode protectors against dendrite growth and chemical/electrochemical corrosion. In this review, we mainly focus on the application of various carbon‐based materials in Na‐O2 batteries and highlight their advances. The scientific understanding on the fundamental design of the material microstructure and chemistry in relation to the battery performance are summarized. Finally, perspectives on enhancing the overall battery performance based on the optimization and rational design of carbon‐based cell components are also briefly anticipated.