Micropyretic synthesis technique employs self-sustaining exothermic (combustion) reactions for the preparation of various ceramic, intermetallic, and composite materials. In the present work, the combustion reactions of Mo and Si with Al additions have been systematically studied. The atomic mixtures of the reactant powders are chosen to be Mo + (2 − x)Si + xAl with x = 0−0.4. In comparison with the Mo + 2Si reaction which leads to the formation of MoSi2, the substitution of Al for Si decreases the sample ignition temperature, but increases the intensity of the combustion reactions. In addition, the substitution of Al for Si results in the formation of a ternary intermetallic phase, called molybdenum alumino-silicide Mo(Si, Al)2, in the synthesized product. When the content of Al in the reactant mixtures reaches 0.4, nearly single phase Mo(Si, Al)2 is obtained and no MoSi2 is detected in the reaction product. These influences are analyzed by using x-ray diffraction (XRD), scanning electron microscopy (SEM), and differential thermal analysis (DTA). The effect of Al additions on the reaction mechanism is also discussed.