The presence of the methylhydrosilyl segments within the poly(diphenylsilane) chain lead to important conformational changes and the formation of elemental silicon particles. To investigate these processes polyhydrosilanes with various contents of methylhydrosilyl groups were synthesized by homogeneous coupling of methyldichlorosilane with diphenyldichlorosilane. Spectral analysis techniques combined with atomic force and polarized light microscopy were used to elucidate the mechanism of the silicon particle formation within the polymeric matrix.