Sulfur hexafluoride (SF6) is widely used in the power industry due to its excellent insulation and arc-extinguishing properties. However, its strong greenhouse effect makes it imperative to reduce SF6 emissions. In the field of SF6 degradation, the use of catalyst filling has been shown to significantly enhance the degradation efficiency. In this study, a dielectric barrier discharge (DBD) system filled with a TiO2 catalyst was designed to investigate the degradation of SF6. The effect of the TiO2 catalyst on SF6 degradation within the DBD system was systematically studied. Experimental results showed that the SF6 degradation rate increased with rising input power. At an input power of 110 W, the degradation rate of SF6 reached 85.3% in the TiO2-catalyzed system. As the input power increased from 70 W to 110 W, the system’s energy yield first increased and then declined. The highest energy yield of 18.95 g/kWh was achieved at 80 W, while it decreased to 14.48 g/kWh at 110 W. The main degradation products of SF6 were SO2, SO2F2, SOF2, and SOF4, with SO2F2 being the most abundant and SOF4 the least. This study provides experimental evidence for the degradation of SF6 exhaust gas and offers guidance for its potential industrial application.