V-Si-B and Mo-Si-B alloys are currently the focus of materials research due to their excellent high temperature capabilities. To optimize the mechanical alloying (MA) process for these materials, we compare microstructures, morphology and particles size as well as hardness evolution during the milling process for the model alloys V-9Si-13B and Mo-9Si-8B. A variation of the rotational speed of the planetary ball mill and the type of grinding materials is therefore investigated. These modifications result in different impact energies during ball-powder-wall collisions, which are quantitatively described in this comparative study. Processing with tungsten carbide vials and balls provides slightly improved impact energies compared to vials and balls made of steel. However, contamination of the mechanically alloyed powders with flaked particles of tungsten carbide is unavoidable. In the case of using steel grinding materials, Fe contaminations are also detectable, which are solved in the V and Mo solid solution phases, respectively. Typical mechanisms that occur during the MA process such as fracturing and comminution are analyzed using the comminution rate K P . In both alloys, the welding processes are more pronounced compared to the fracturing processes.