SF₆ is a strong greenhouse effect gas, which is widely used in high-voltage electrical equipment such as circuit breakers and high-voltage switchgear because of its excellent insulation performance and arc extinguishing ability. In recent years, the use and emission of SF₆ have been rising, and with the proposal of the dual carbon strategic goal, its harmless degradation has become an urgent problem to be solved. In this paper, SF₆ was degraded by pulsed DBD plasma technology and O₂. Studies have shown that the addition of O₂ can effectively promote the degradation of SF₆. With the increase in the added O₂ content, the DRE and EY of SF₆ first increased and then decreased. Under the conditions of the input power of 50 W, SF₆ concentration of 2%, and gas flow rate of 50 mL/min, the reaction system obtained the highest DRE and EY of 58.40% and 5.24 g/kWh when the O₂ content was 1%, respectively. In the SF₆/Ar/O₂/H₂O system, the addition of H₂O could improve the product selectivity of SO₂F₂, and when the O₂ concentration was 1%, the highest selectivity of SO₂F₂ was 48.96%, and the concentration was 8006.76 ppm. The addition of O₂ inhibited the production of SO₂, and with the addition of the O₂ system, SO₂F₂ and SOF₄ were the main components of degradation products; however, there were also SOF₂, SO₂, SiF_4, SF₄, etc. In this paper, the decomposition path of O₂ under SF₆ was analyzed in detail according to infrared spectroscopy and decomposition products.