It has become increasingly clear that deviations from local thermodynamic equilibrium occur in thermal plasmas. This paper is devoted to investigating the non-equilibrium characteristics of CO2 thermal plasmas, which have wide application in industry. A two-temperature chemical kinetic model with a comprehensive chemical system is developed to calculate the non-equilibrium characteristics of CO2 thermal plasmas for a wide temperature range, from 12,000 to 500 K, at atmospheric pressure. The non-equilibrium results are compared to the equilibrium composition obtained by Gibbs free energy minimization, and significant deviations are found at lower temperatures. Based on the dependence of molar fractions on temperature, the dominant species are determined in three temperature ranges. The dominant reactions are then obtained by considering their contribution to the generation and loss of the dominant species. Using the dominant species and reactions, the full model is simplified into three simpler models and the accuracy of the simplified models is evaluated. It is shown that this approach greatly reduces the number of species and reactions considered, while showing good agreement with the full model, with a root-mean-square error of no more than 4 %. Thus, the complicated physicochemical processes in non-equilibrium CO2 thermal plasmas can be characterized by relatively few species and reactions. It is suggested that the two-temperature chemical kinetic model developed in this paper can be applied to the full range of pressures that occur in arc welding, arc quenching and other industrial applications. In addition, the simplified methods can be applied in multi-dimensional models to reduce the chemical complexity and computing time while capturing the main physicochemical processes in non-equilibrium CO2 thermal plasmas.