A new dialdehyde-containing silicon was prepared by a reaction of Williamson-type and structurally characterized. By its subsequent condensation with 2,5-bis(p-aminophenyl)-1,3,4-oxadiazole, a multifunctional polyazomethine-containing imine, phenylene, oxadiazole, ether, and carbosilane groups within the chain was prepared. The complexes of this polymer with Co(II), Cu(II), and Zn(II) ions formed on the basis of electron-donor ability of the oxadiazole and azomethine groups were prepared in a one-step approach by mixing the two precursors of polyazomethine (dialdehyde and diamine) with corresponding metal salt. The ligand and metal complexes were characterized by spectral (Fourier transform infrared (FTIR), 1H, and 13C NMR) methods. The thermal, optical, electrochemical, and dielectric properties were studied and the effects of the metal insertion in dependence on its nature over these properties were evaluated. All compounds are soluble in common organic solvents and show low glass transitions due to the flexible ether and Si–C bonds, are fluorescent, mainly due to the oxadiazole ring, are redox active and have high dielectric constant due to the presence of oxadiazole, azomethine metal units.