SFC (Sillico-Ferrite of Calcium) is a kind of simplified SFCA (Sillico-Ferrite of Calcium and Aluminum) with no Al2O3. SFC and SFCA are believed to be the most desirable bonding phase in sinter. In order to better understand the fundamentals of the reduction of SFC, a series of experiments on the SFC reduction were carried out in the present work, including phase equilibria tested by XRD, morphology tested by SEM-EDS, and reduction pathway under the different CO/CO2 mixture gas at 1000°C. The experimental results indicated, (1) in the case of CO = 20% and 40%, most of Fe2O3 in SFC was reduced to FeO. The equilibrium phases were FeO, CaO·Fe2O3, and CaO·SiO2. (2) In the case of CO = 60%, CaO·Fe2O3 was reduced to generate FeO and 2CaO·Fe2O3. The equilibrium phases were FeO, 2CaO·Fe2O3, and CaO·SiO2. (3) In the case of CO = 80% and 90%, FeO was reduced to Fe, and 2CaO·Fe2O3 was reduced to generate Fe and CaO. The equilibrium phases were Fe, CaO, and CaO·SiO2. The findings from this work may provide guidelines for the improvement of sintering production and blast furnace performances.