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The gas mixture CO2–O2 has been considered as an insulation and arc-quenching medium in gas-insulated switchgears. In this paper, the dielectric breakdown properties of CO2–O2 mixtures at different O2 concentrations and gas pressures were studied theoretically by considering ion kinetics in a spatial–temporal growth avalanche model. A kinetic scheme that includes all the main reactions likely to occur in CO2–O2 mixtures is presented. An improved method to calculate the dielectric strength of the gas mixture is developed, based on an avalanche model that considers both spatial growth and temporal processes. Next, the reaction rates of ionization, attachment, detachment and ion conversion, the effective ionization Townsend coefficient αeff/N, and reduced critical electric field strength (E/N)cr in CO2–O2 mixtures at different mixing ratios and gas pressures are analyzed in detail. Finally, a pulsed Townsend experiment is performed to verify the validity and accuracy of the calculation method. Based on this, one detachment reaction rate is modified to yield more accurate results. Better consistency between the results and the experimental values supports the validity of the kinetic system, reaction rates, and the improved calculation method. [ABSTRACT FROM AUTHOR]