Eight coordination polymers (CPs), {[Ag(L1)]ClO 4 } n (1), {[Ag(L2) 1.5 ]ClO 4 ·C 2 H 3 N} n (2a), {[Ag(L2)]ClO 4 } n (2b), [Zn(L1)Cl 2 ] n (3), {[Zn(L2)Cl 2 ]·CHCl 3 } n (4), {[Cu(L1) 2 Cl]Cl·H 2 O} n (5), [Cu 2 (L2)(µ-Cl) 2 ] n (6) and [Cu 4 (L2)(µ-Cl) 4 ] n (7) were synthesizedvia self-assembly of corresponding metal ions and biimidazole based ditopic ligands, 1,1´bis(pyridin-3-ylmethyl)-2,2´-biimidazole L1 and 1,1´-bis(pyridin-4-ylmethyl)-2,2´-biimidazole L2. These ligands possess conformational flexibility and two pairs of coordination sites: pyridine nitrogen (N Py ) atoms and imidazole nitrogen (N Im ) atoms. Depending on the metal center in CPs, the biimidazole compounds act as tetra -(1, 7), tri-(2a) or bidentate (2a, 2b, 3-6) ligands binding to the metal either via N Py or N Im , or both. All these CPs were structurally fully characterized with single crystal X-ray structure, mass spectrometry, and NMR spectroscopy. The solid state photophysical properties and thermal stabilities of the CPs were also briefly studied in the solid state.