Pellet ore is an important raw material for blast furnace ironmaking, and its reduction and expansion performance directly affects the smooth operation and smelting indicators of the blast furnace. This paper quantitatively studied the effects of magnesium minerals such as dolomite and serpentinite on the pellet-forming performance, the microstructure after roasting, compressive strength, and the reduction expansion performance of Baiyun Ebo iron concentrate. The optimal ratio of dolomite and serpentinite to add was determined when preparing pellets using Baiyun Ebo iron concentrate powder. The results showed that the drop strength and compressive strength of the green pellet after adding serpentine were relatively higher than those after adding dolomite, indicating that controlling the MgO content in the green pellet at 2.5% using serpentine was beneficial for improving the drop strength and compressive strength. Under the condition of adding dolomite, when the MgO content was 2.5%, the compressive strength of the roasted pellet was the highest, which was 2192.6 N, and the volume expansion rate was 12.32%. Under the condition of adding serpentine, when the MgO content was 2.5%, the compressive strength of the roasted pellet was 2622.2 N, and the volume expansion rate was 9.71%. Compared with dolomite as a magnesium additive, when the reduction expansion rate of Baiyun Ebo iron concentrate was controlled within 20%, serpentine only needed to have a MgO content of about 1.5% in the pellets, while dolomite needed to have a MgO content of about 2.5%. Therefore, under the condition that the MgO contents of dolomite and serpentine were equivalent, the amount of serpentine used was lower.