Molybdenum-based thermal spray powder is widely used for coating the moving parts of the internal combustion engines due to its excellent wear resistance. A composite powder of the Mo 40 (Al 1?x Si x ) 60 system was synthesized using the SHS method. The synthesized bulk was pulverized and specially treated to produce thermal spray powder. It was found that the synthesis reaction consisted of two-steps: the formation of Al 8 /Mo 3 and the formation of Mo(Al,Si) 2 . Both the temperature and the rate of the SHS reaction linearly increased with the increase of the value of x in Mo 40 (Al 1?x Si x ) 60 , The temperature and the rate of the reaction were also affected by the compacting density of the specimens, exhibiting the maximum valves at 62% and 60%, respectively. Since spherical shape is advantageous to the thermal spraying process, shape-control of the powder was attempted with PVA as a binding additive, resulting in the successful production of almost perfectly spherical powder of 80 μm Ø (d 50 ) mean particle size.