Organometallic polymers containing Pd atoms in different co-ordination sites were obtained and characterized. The reactions were performed in a wide range of complex/monomer molar ratios. Functionalized monosubstituted acetylenes, namely propargyl alcohol (POH) and N,N-dimethylpropargylamine (DMPA) undergo coordinative polymerization in the presence of the corresponding bis(triphenylphosphine)bis(acetylide) Pd(II) complexes, [Pd(PPh3)(2)(C=C-CH2OH)(2)] and [Pd(PPh3)(2)(C=C-CH2N (CH3)(2))(2)]. The complexes are active catalysts for the activation of the C-C bond of acetylenic monomers, leading to a pi-conjugated C=C backbone. By increasing the complex/monomer ratios, interaction of Pd with the C=C double bonds of neighbour chains and with the polymer pendant groups also occurs.