The hydrosilylation of phenylacetylene with triethoxysilane catalyzed by polymer-supported Rh(I) and Pt(II) complexes has been investigated. Polyamides having the 2,5- and 2,6-pyridine moiety in their repeat units were used as the catalysts supports. The effect of the support structure, the type of solvent used, the substrate ratio and catalyst concentration on reaction selectivity were studied. X-ray photoelectron spectroscopy (XPS) was used to characterize the polymer supports and the supported catalysts before and after use. It was found that the selectivity of the hydrosilylation can be controlled by the chemical structure of the polymer support. When the reaction was catalyzed by Rh(I) attached to the polyamide with a pyridine substituted in the 2,6 position, beta(Z)-vinylsilane was formed as the major product. Use of the same catalyst supported on the polymer with the 2,5-pyridine resulted in a reversal of the stereoselectivity and beta(E)-vinylsilane was the major product. These results have been correlated with the reaction mechanism and the electron density on the rhodium centres. The binding energy for the Rh3d 5/2 attached to the 2,6-py moiety was found to be lower by 1.03 eV than that for the Rh supported on the 2,5-py type polymer. Hydrosilylation using Pt(II) as the catalyst supported on the same series of polyamides proceeded in the usual manner of cis addition to give predominantly beta(E)-vinyl product and the alpha-isomer. The only difference caused by the presence of the polymer support was the increased yield of alpha-product. Recycling tests demonstrated high stability of the supported catalysts during prolonged use.