The CO2 conversion rate and conversion efficiency were greatly enhanced by homogeneous dielectric barrier discharges generated in our experiment. Influence of CaO-B2O3-SiO2 glass addition on dielectric properties and microstructures of Ca(0.8)Sr(0.2)TiO3 were investigated for the purpose of discerning the effect of dielectric barrier material on the dielectric barrier discharge performance so as to improve the CO2 conversion rate and conversion efficiency. It was found that considerable grain boundaries on the dielectric barrier surface serving as charge trapping sites contribute a great many charges during plasma generation. And low resistance of the dielectric barrier surface distributes the charges effectively. More importantly, when the gap of the discharge is narrowed down, the surface charges on the dielectric barrier will play a dominant role during the discharge. As a result, for the 5.0 wt% glass addition, the CO2 conversion rate and conversion efficiency reached the maximum values of 48.71 % and 1.14 W/%, respectively.