Telechelically bis(hydrodimethylsilyl)-functionalized oligo(dimethylsiloxane)s or aromatics were found to give polymers constituting of alternating disilylene and oligodimethylsiloxane or 4,4′-diylaromatics as repeating units by dehydrogenative coupling reaction in the presence of palladium dibenzylideneacetone complex. The same catalyst gave polysilylenes with trisiloxane pendant from 1,1-dihydro-1,3,3,5,5,7,7,7-octamethyltetrasiloxane.