Mo-ZrO2 alloy was prepared by ball milling, solid-liquid synthesis and powder metallurgy, and the molten glass erosion resistance test was carried out. The effect of amount of addition of ZrO2 on the molten glass erosion resistance of the Mo-ZrO2 alloy was studied. The results show that ZrO2 significantly refines molybdenum grains, and hinders the growth of molybdenum grains under the erosion of high temperature glass melt. Doping ZrO2 greatly reduces the erosion depth of glass melt. The interfacial morphology analysis shows that the good resistance to glass melt erosion of Mo-ZrO2 alloy is due to the “synergistic effect” between the molybdenum matrix and the second phase particle ZrO2. ZrO2 cements the grain boundary with the molybdenum matrix to prevent the erosion of glass melt on the molybdenum matrix, and the molybdenum matrix supports the ZrO2 particles to prevent the spalling of ceramic phase.