Three new Cu(II) supramolecular complexes [Cu( L 1 )Cl 2]·2DMF ( 1), [Cu( L 2 )Cl 2] ( 2) and [Cu( L 3 )Cl 2]·DMF ( 3) ( L 1 = 3,3′-bis(2-benzimidazolyl)-2,2′-dipyridine, L 2 = 3,3′- bis(N-ethyl-2-benzimidazolyl)-2,2′-dipyridine and L 3 = 3,3′-bis(N-benzyl-2-benzimidazolyl)-2,2′-dipyridine) have been prepared and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. X-ray structural analysis of L 1 , L 2 ·3.5H 2O and L 3 ·H 2O indicates that all three ligands adopt the trans conformation with the two benzimidazole fragments located on opposite sides of the dipyridyl backbone. While in complexes 1– 3, all the ligands display the cis conformation and behave as bidentate chelating reagents to coordinate with Cu(II). The inorganic chloride ions always act as a reliable hydrogen bonded acceptor in these structures, and the resulting C–H⋯Cl 2Cu supramolecular synthons play a significant role in the formation and stabilization of the structures. Moreover, additional non-covalent interactions, such as C–H⋯π, are also identified to extend the discrete (0-D) or low-dimensional (1-D) motifs into high-dimensional architectures.