Polyorganosilanes are prepared by contact reaction of organodihalosilanes with alkali metal fine particles in an organic solvent. Prior to the contact reaction, a triorganohalosilane is contacted with the dispersion of alkali metal fine particles in organic solvent for removing reactive oxygen and moisture from the dispersion. Formation of a siloxane bond in the polysilane backbone is minimized, and polyorganosilanes having a minimal oxygen content are obtained.
