H-bonded supramolecular polymers based on 1,3-bis(3-carboxypropyl)tetramethyldisiloxane and 4,4′-azopyridine, 1, or imidazole, 3, were prepared and used as ligands for Co(II) and Zn(II) ions, respectively. A re-organization of the supramolecular structures occurred by introducing the metal salts, Co(ClO 4 ) 2 × 6H 2 O and Zn(O 2 CCH 3 ) 2 × 2H 2 O, leading to the polyorganometallosiloxane structures 2 and 4, respectively. The compounds were investigated by elemental and spectral ( 1 H NMR, FTIR, UV–Vis, and fluorescence) analysis as well as by X-ray single crystal diffraction. Thermal behaviour of the metallopolymers was evaluated by TGA and DSC while the moisture behaviour was studied by dynamic vapour sorption analysis (DVS). Magnetic susceptibility was determined for paramagnetic Co(II)-containing polyorganometallosiloxane. The dielectric response and ac conductivity were investigated by dielectric spectroscopy at different temperatures and frequencies.