Supramolecular liquid-crystalline main-chain polymers have been obtained by self-assembly of non-mesomorphic bifunctional ligands and a transition metal ion. Stilbazole dimers, bis[2-(2-{4-[2-(4-pyridyl)vinyl]phenoxy}ethoxy)ethyl] ether (1) and 1,2-bis[2-(2-{4-[2-(4-pyridyl)vinyl]phenoxy}ethoxy)ethoxy]benzene (2) have been synthesized and complexed with silver trifluoromethanesulfonate (CF3SO3Ag). The metallomesogenic polymeric complexes formed by coordination bonds between the pyridyl groups of the stilbazole dimers and the silver ion exhibit smectic phases.