<p>Sulfur dioxide (SO₂) emissions, a major source of air pollution, can be effectively mitigated through catalytic reduction to elemental sulfur using carbon monoxide (CO). In this study, Fe loaded TiO₂ catalysts were synthesized and subsequently subjected to pre-sulfurization treatment under varied conditions. Their catalytic performance was evaluated in SO₂ reduction for thermal and dielectric barrier discharge (DBD) plasma enhanced thermal catalysis. The results showed that OFS-Fe/TiO₂ catalyst with oxygen-free sulfurization (OFS) treatment exhibited the highest catalytic activity, achieving above 90% SO₂ conversion between 250 and 550&#xa0;°C under oxygen-assisted reaction (OAR), along with long-term stability under 40–60% water vapor. However, the SO₂ conversion were below 20% for Fe/TiO₂ and oxygen-assisted sulfurization OAS-Fe/TiO₂ catalysts within 250 to 400&#xa0;°C. Notably, the significantly enhanced catalytic performance of the OFS-Fe/TiO₂ catalyst was probably attributed to the high dispersion of Fe over nano-TiO₂, the lower Fe²⁺/Fe³⁺ ratio, and the formation of active FeS₂ species detected by SEM-EDS, XPS and TPD techniques. Furethermore, a conversion efficiency exceeding 90% was maintained throughout 80 to 550&#xa0;°C under DBD plasma reaction over POFS-Fe/TiO₂ catalyst with room-temperature DBD plasma oxygen-free sulfurization treatment, surpassing thermal catalysis performance. The significantly enhanced low-temperature activity of plasma catalysis was attributed to the lowest Fe²⁺/Fe³⁺ ratio, together with the transformation of FeS₂ into FeS, generating more sulfur vacancies. In-situ DRIFTS experiments confirmed two distinct SO₂ adsorption and reduction mechanisms between Fe/TiO₂ and OFS-Fe/TiO₂ catalysts. The results demonstrate that pre-sulfurization and plasma modification serve as an effective catalytic strategy to enhance CO-mediated SO₂ reduction, offering a sustainable emission control approach through sulfur resource utilization.</p> Graphical Abstract <p></p>