Solid state Na-CO2 batteries are a kind of promising energy storage system, which can use excess CO2 for electrochemical energy storage. They not only have high theoretical energy densities, but also feature a high safety level of solid-state batteries and low cost owing to abundant sodium metal resources. Although many efforts have been made, the practical application of Na-CO2 battery technology is still hampered by some crucial challenges, including short cycle life, high charging potential, poor rate performance and lower specific full discharge capacity. This paper systematically reviews the recent research advances in Na-CO2 batteries in terms of understanding the mechanism of CO2 reduction, carbonate formation and decomposition reaction, design strategies of cathode electrocatalysts, solid electrolytes and their interface design. In addition, the application of advanced in situ characterization techniques and theoretical calculation of metal–CO2 batteries are briefly introduced, and the combination of theory and experiment in the research of battery materials is discussed as well. Finally, the opportunities and key challenges of solid-state Na-CO2 electrochemical systems in the carbon-neutral era are presented.