Fe₂O₃ as a catalyst for H₂S oxidation, has a high catalytic activity but a low sulfur selectivity. In this regard, a series of Fe₂O₃ supported on UiO-66 complex catalysts (xFe₂O₃@UiO-66, x represents the weight percentage of Fe₂O₃) with high sulfur selectivity were successfully synthesized, and their catalytic performance was investigated at varied reaction temperature (100–210 ℃). The experimental results indicate that 5Fe₂O₃@UiO-66 catalyst shows the best catalytic performance at 150 ℃, the H₂S conversion keep at 100% and the sulfur selectivity reaches 93.06%, which is significantly higher than the bulk Fe₂O₃ (62%) and commercial Fe₂O₃ (80%). The superior catalytic performance is mainly attributed to the synergistic effect between Fe₂O₃ and UiO-66, the formed FeOZr bonds help the electrons transfer from Fe to Zr, which inhibits the formation of the intermediate of FeS₂ during the catalytic process, a species that readily to be oxidized into SO₂, thus promotes its sulfur selectivity. In addition, the high specific surface area, abundant pores and the high dispersion of Fe₂O₃ nanoparticles also contributed to its improved sulfur selectivity. The deposition of elemental sulfur and sulfates responsible for its deactivation.