The direct activation of undiluted CO2 is carried out in a co-axial dielectric barrier discharge (DBD) reactor. The variation of the electrical discharge parameters and their influence on CO2 decomposition is investigated with the integration of 15 % MO/γ-Al2O3 (M = Ni, Cu) catalyst in the discharge zone. The electrical discharge is found to shift from the filamentary to a combination of surface and micro filamentary discharge on catalyst integration to NTP and also leads to the higher conversion of CO2 than DBD alone. The highest conversion of CO2 (15.7 %) with the energy efficiency of 1.597 mmol/kJ is achieved under CuO/γ-Al2O3 integrated NTP system, whereas the maximum of carbon balance (94.4 %) reaches with 4% CeO2 addition to CuO/Al2O3 catalyst. The oxygen vacancy of the catalyst plays a vital role in improving the performance, especially, the oxygen buffer property of CeO2 facilitates the recombination reaction and contributes to obtaining the highest carbon balance. © 2020 Elsevier Ltd.