Organic/inorganic hybrids of silicon and their subsequent chemical modification are of interest for tailoring and structuring surfaces on the nanoscale. The formation of monolayers on hydroxylated silicon surfaces was employed to synthesize molecular dimethylsiloxane chains by wet-chemical condensation reactions, using dimethylmonochlorosilane as the precursor. The SiH group of the resulting dimethylsilyl termination could be selectively oxidized to the SiOH group, which opened the possibility of bonding another species. By repeating the condensation and oxidation cycle the stepwise growth of one-dimensional dimethylsiloxane chains was achieved. The ongoing chain growth was characterized by attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy, x-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE), and determination of the surface energy by contact-angle experiments.