Three new polymeric complexes of cadmium(II) with imidazole and its derivatives [imidazole (Im), benzimidazole (Bim) and 1-methylimidazole (Mim)] mediated by thiocyanate and dicyanamide (dca) anions have been synthesized and characterized by X-ray single crystal structure analysis. The structure analyses reveal that complexes [Cd(SCN)2(Bim)2]n (1) and [Cd(dca)2(Im)2]n (2) are 1D coordination polymers, whereas complex [Cd(dca)2(Mim)2]n (3) adopts a 2D network of (4, 4) topology and thereby suggests that the dimensionality of the coordination polymers are affected by the choice of the counter anions and by the organic ligands. All the species exhibit interesting luminescence property in methanol and in solid state originated from ligands-centered π-π* transitions. The π-π interactions occurring between organic rings (Im, Mim, and Bim) are observed to be important in controlling the fluorescence property of the species. © 2010 Elsevier Ltd. All rights reserved.