Rapid industrialization has resulted in significant gaseous sulfur dioxide (SO2) pollutant emissions, which come from power plants, petrochemical industries, and metallurgical plants. This toxic, non-inflammable, and notorious pollutant poses a threat to ecosystems, contributes to acid rain formation, and leads to the corrosion of equipment and infrastructure. Catalytically reducing SO2 to elemental sulfur, which is a benign and valuable product, in a reducing atmosphere is a promising solution. It has gained considerable attention not only for the SO2 emission reduction, but also for the resource utilization of SO2 waste gas. In this study, iron doping perovskite materials (denoted as LaCo0.8Fe0.2O3) were synthesized by the citric acid induced sol-gel method followed by calcination at a certain temperature. The material was subjected to oxygen-free sulfurization (which is denoted as OFS-LaCo0.8Fe0.2O3) and oxygen free sulfurization under dielectric barrier discharge (DBD) plasma conditions (which was denoted as POFS-LaCo0.8Fe0.2O3). X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and scanning electron microscopy (SEM) were used to analyze the structure and properties of the catalytic materials. The performance of sulfur production by DBD thermal-catalytic reduction of SO2 under CO, and combined CO and H2 reducing atmospheres was investigated, together with the by-products under different catalytic materials and varied reducing gas conditions. The XRD results showed that both OFS-LaCo0.8Fe0.2O3 and POFS-LaCo0.8Fe0.2O3 maintained the perovskite crystal form with a weaker decrease in peak intensity compared to LaCo0.8Fe0.2O3. After catalytic reaction with SO2, the XRD pattern exhibited other weak impurity peaks. With CO reduction, compared with DBD reduction alone, the combination of DBD plasma and the catalyst increased the SO2 conversion rate from 82.3% to 95.0% at 450℃. In addition, the SO2 conversion rate reached 99.8% under co-reduction with CO and H2 at 300℃. The H2-TPR results indicated that the reduction peak of LaCo0.8Fe0.2O3 showed better reducibility at lower temperatures compared to OFS-LaCo0.8Fe0.2O3, which may contribute to the increased SO2 conversion.