With coal gas as a reducing agent, the catalytic reduction of SO2 to sulfur in the flue gas produced in metallurgical processes was studied over catalysts of rare earth-Fe/Al2O3 (REFe/Al2O3). The catalytic activity of the REFe/Al2O3 catalyst on the reduction of SO2 to sulfur was investigated based on kinds and the contents of rare earths and different preparation method of the catalyst. Additionally, the mechanism of this catalytic reduction reaction was also explored. Results showed that different rare earth imposed different effect on the activity of the Fe/Al2O3 catalyst. Especially, the addition of Sm and Dy greatly improved the catalytic activity of Fe/Al2O3. The yield of sulfur over SmFe/Al2O3 was increased to 86.62% at 360 °C, which was 40.5% higher than that over Fe/Al2O3 at the same temperature; and the sulfur yield over DyFe/Al2O3 was increased to 91.62% at 400 °C, 26.4% higher than that over Fe/Al2O3. The catalytic activity of REFe/Al2O3 was somehow dependent on the content of rare earth. For SmFe/Al2O3, the content of Sm was optimized to be about 1.0 wt.%. The rare earth catalyst prepared with different methods also showed varied activity. The sulfur yield over rare-earth transition metal catalysts follows the order: Sm and iron solution mixing impregnation>Sm first, then iron solution impregnation>iron first, then Sm solution impregnation. The reaction mechanism of SO2 reduction to sulfur with coal gas was proposed to be an intermediate mechanism. With coal gas as a reducing agent, the catalytic reduction of SO2 to sulfur in the flue gas produced in metallurgical processes was studied over catalysts of rare earth-Fe / Al2O3 (REFe / Al2O3). The catalytic activity of the REFe / Al2O3 catalyst on the reduction of SO2 to sulfur was investigated based on kinds and the contents of rare earths and different preparation method of the catalyst. Especially, the addition of Sm and Dy greatly improved the catalytic activity of Fe / Al2O3. The yield of sulfur over SmFe / Al2O3 was increased to 86.62% at 360 ° C, which was 40.5% higher than that of over Fe / Al2O3 at the same temperature; and the sulfur yield over DyFe / Al2O3 was increased to 91.62% at 400 ° C, 26.4% higher than that over Fe / Al2O3. The catalytic activity of REFe / Al2O3 was somehow dependent on the conten The rare earth catalyst prepared with different methods also showed varied activity. The sulfur yield over rare-earth transition metal catalysts follows the order : Sm and iron solution mixing impregnation> Sm first, then iron solution impregnation> iron first, then Sm solution impregnation. The reaction mechanism of SO2 reduction to sulfur with coal gas was proposed to be an intermediate mechanism.