MgO clinker and two kinds of dolomite clinkers with different microstructures and CaO contents were used as starting materials, and the effects of Fe2O3 addition on the properties of MgO and dolomite were investigated in the range of 2 to 8 wt% of Fe2O3 content. Secondary phases contributed to densification of MgO-Fe2O3 and dolomite-Fe2O3 were magnesioferrite and dicalciumferrite, respectively. Sinterabilities of MgO-Fe2O3 and dolomite-Fe2O3 were directly proportional to the amount of secondary phases. Also, sinterability of dolomite itself was dependent on the microstructure of starting material including distribution of CaO and MgO as well as the addition amount of Fe2O3. The flexural strength of MgO-Fe2O3 content was almost constant. The hydration resistance of dolomite with large size of MgO and discontinuous distribution of CaO was higher than that of dolomite with small size of MgO and continuous distribution of CaO. Also, the minimum content of Fe2O3 to prevent they hydration of dolomite was about 4wt%. As increasing Fe2O3 content, the penetration resistance of MgO-Fe2O3 was improved by the increment of magnesioferrite. On the other hand, the penetration resistance of dolomite-Fe2O3 was decreased because of the increment of dicalciumferrite having low melting point.