Sulfur hexafluoride, SF6, is a common dielectric medium for high-voltage electrical equipment, but because it is a potent greenhouse gas, it is important to find less environmentally harmful alternatives. In this paper we explore the use of CO2 and O2 as one alternative. We studied the synergistic effect in a mixture of CO2 and O2 from both macroscopic and microscopic perspectives. The effect leads to a dielectric strength of the mixture being greater than the linear interpolation of the dielectric strengths of the two isolated gases. We analyzed the critical reduced electric field strength, (E/N)cr, the breakdown gas pressure reduced electric field, E/p, and the breakdown electron temperature, Tb, and their synergistic effect coefficients for various CO2 concentrations and various products of the gas pressure times the gap distance (pd). A gas discharge and breakdown mechanism in a homogenous electric field is known to be controlled by the generation and disappearance of free electrons, which strongly depend on the electron temperature. The results indicate that adding a small amount of O2 to CO2 can effectively improve the value of (E/N)cr and bring a clear synergistic effect. In addition, significantly different variation trends of the synergistic effect in the E/p and Tb of CO2-O2 mixtures at various CO2 concentrations and pd values were also observed.