Dehydrocoupling reactions between linear poly(methylhydrosiloxane) {Me3SiO-[MeSi(H)O](n)-SiMe3} and alcohols such as cholesterol, anthracene-9-carbinol, (12-crown-4)-2-carbinol, pyrene-1-carbinol, 4-methyl-5-thiazoleethanol, and 4-pyridil-propanol were introduced under catalytically mild conditions. The degrees of conversion of Si-H bonds in polysiloxane were monitored with H-1 NMR spectra. The reaction of the 9-methoxyanthracene adduct on siloxane polymers and maleimide derivatives (maleimide, N-ethylmaleimide, and maleic acid anhydride) produced [2+4]-cycloadducts in very high yields.