In general, semiconductor materials for thermoelectric generation prepared by vacuum metallurgy shows a relatively high value of figure-of-merit. However, differences in some properties of alloys elemental constituents can cause processing problems. Recently, Mechanical Alloying (MA) has been used to produce polycrystalline thermoelectric materials, such as (Bi,Sb)2 and (Te,Se)3(1). The industry is using this process since early 70’s to produce oxide dispersion strengthened alloys and those with widely different melting temperatures (2) In the present work, Si0.80Ge0.20 alloys were prepared via Mechanical Alloying (MA), using 99.9 % pure silicon and germanium powders, with a sieve size of 100 mesh. The MA has been performed, for several balls - to - powder ratio, in a SPEX 8000 vibratory high energy milling with tungsten carbide balls. Time for alloy formation was in a range from 3 to 9 hours, corresponding to charge ratio of 12:1 and 4:1, respectively. After two hours of processing time, the grinding temperature reached 80 0 C, and remained at this level until the end of the process. It was possible to follow the SiGe alloy formation by x-ray diffractometry, as the peak lines positions of elemental Si and Ge were continuously shifted, and end up to merge into a single broad peak. There was a convergence of the individual lattice parameters of Si and Ge to a single value of 5.470 A, measured within the limit of 0.005 A. For the Si0.80Ge0.20 system evaluated in this work, the alloying progress occurred continuously, and changed inversely with charge ratio.