AbstractLow‐molecular‐weight organosilane polymers were prepared by sodium coupling of dichloro‐methylphenylsilane (1) with chlorotrimethylsilane (2). Gel permeation chromatography (GPC), IR and NMR (1H,13C and29Si) analysis of the crude product (3) were performed and compared with those of the isolated first oligomers, trisilane (3a) and tetrasilane (3b). The GPC characteristics, especially high resolution ones, in accordance with the α,ω‐bis(trimethylsilyl)‐oligo(methylphenylsilane) structure are compared with those of hydrocarbon polymers. The relations of the NMR characteristics of the methylphenylsilanediyl unit with the position along the chain and the configuration of the diads are approached. Some spectroscopic indications of the secondary structure ar