This work explores the effect of N 2 addition on CO 2 dissociation and on the vibrational kinetics of CO 2 and CO under various non-equilibrium plasma conditions. A self-consistent kinetic model, previously validated for pure CO 2 and CO 2 –O 2 discharges, is further extended by adding the kinetics of N 2 . The vibrational kinetics considered include levels up to v = 10 for CO, v = 59 for N 2 and up to v 1 = 2 and v 2 = v 3 = 5, respectively for the symmetric stretch, bending and asymmetric stretch modes of CO 2 , and account for electron-impact excitation and de-excitation (e–V), vibration-to-translation (V–T) and vibration-to-vibration energy exchange (V–V) processes. The kinetic scheme is validated by comparing the model predictions with recent experimental data measured in a DC glow discharge operating in pure CO 2 and in CO 2 –N 2 mixtures, at pressures in the range 0.6–4 Torr (80.00–533.33 Pa) and a current of 50 mA. The experimental results show a higher vibrational temperature of the different modes of CO 2 and CO and an increased dissociation fraction of CO 2 , that can reach values as high as 70%, when N 2 is added to the plasma. On the one hand, the simulations suggest that the former effect is the result of the CO 2 –N 2 and CO–N 2 V–V transfers and the reduction of quenching due to the decrease of atomic oxygen concentration; on the other hand, the dilution of CO 2 and dissociation products, CO and O 2 , reduces the importance of back reactions and contributes to the higher CO 2 dissociation fraction with increased N 2 content in the mixture, while the N 2 (B 3 Π g ) electronically excited state further enhances the CO 2 dissociation.