An aluminothermic reaction starting with inexpensive MoO3, SiO2, and Al powders was utilized to prepare molybdenum disilicide (MoSi2) powders by the micropyretic/combustion synthesis process and leaching. The combustion-synthesized product was porous and could readily be crushed into powders. X-ray diffraction (XRD) analysis revealed that the product of such a reaction consisted of α–Al2O3, MoSi2, and a small amount of Mo(Si,Al)2 and Mo5Si3. The reason for the formation of Mo(Si, Al)2 phase is discussed. MoSi2 powders were obtained by leaching out the Al2O3 from the synthesized powder mixtures in boiling phosphoric acid solution. The synthesized MoSi2 powders, including a small amount of Mo(Si, Al)2 and Mo5Si3, were very fine with an average particle size of about 1 μm.