As one of the most consensus goals around the world, reduction of carbon emissions has attracted huge attention from academic and industry communities for developing renewable energy sources and carbon capture techniques. Nonthermal equilibrium plasma catalysis has been proven to be a very promising way for CO 2 conversion into high-value-added products; however, the synergistic catalytic mechanism between the plasma and various catalysts remains a challenge. In this work, we designed a reactor of atmospheric pressure glow discharge (APGD) plasma jet coupled with V 2 O 5 /TiO 2 nanocomposite catalysts and studied the influence of V 2 O 5 mass fraction, catalyst pretreatment, and reaction plasma parameters on the CO 2 dissociation performance. Results showed that the designed reactor could introduce high-density plasma to the downstream area and maintain lower gas temperature, allowing the collaboration between APGD and the V 2 O 5 /TiO 2 catalyst. The XRD analysis indicated that the solid solution phase TiVO 4 could be formed in catalysts by V 2 O 5 doping and reach a maximal content at a mass fraction of 30%, which determined the most excellent redox ability of the catalyst. The pretreatment of the as-prepared catalyst by Ar dielectric barrier discharge (DBD) plasma increased the oxygen vacancy density of the catalyst, thereby raising the conversion rate by 18.43%. Moreover, the transition regime between laminar and turbulent states was found to be the optimal configuration for CO 2 dissociation. The reaction pathway was proposed for CO 2 dissociation synergistically catalyzed by an APGD plasma jet and V 2 O 5 / TiO 2 . Ultimately, the maximum conversion of 14.88% and energy efficiency of 40.45% were simultaneously achieved, which were superior to the results of most atmospheric pressure plasmas. This work opens an avenue to develop plasma technology for sustainable CO 2 utilization.