A series of mixed halide-dicyanamide and halide complexes of cadmium(II) mediated by 2-aminoalkyl-pyridine ligands [2-aminomethylpyridine (ampy) and 2-aminoethylpyridine (aepy)] have been synthesized. Five of them, [CdCl(dca)(aepy)]n (1), [CdBr(dca)(ampy)]n (2), [CdCl(dca)(ampy)]n (3) (dca = dicyanamide); [CdI2(aepy)]n (4), and [CdI2(ampy)]n (5), (dca = dicyanamide) have been characterized by X-ray single crystal structure analysis. The structural determination shows that the compounds are 1D coordination polymers, with the exception of 3 that gives origin to a 2D sheet-like network. The ampy and aepy ligands (also with the occurrence of dca anions in 1-3) reveal to be useful ancillary fragments for the construction of unprecedented Cd-halide polymeric species. The crystal packing shows that the dimensionality of all compounds is enlarged to 2D, and 3D in the case of complex 3, through π-π interactions occurring between the pyridine rings. All the species exhibit interesting luminescence property in solution as well in solid state which is originated from ligand-centered π-π* transitions. The fluorescence band maxima and fluorescence efficiency (in methanol) are found to be dependent not only on the pyridine ligand but also on the type of halide, and the co-ligand. Solid state luminescent study implies that π-π interactions occurring between pyridine rings are also important in controlling the fluorescence intensity. Amongst the synthesized complexes reported, complex 5 exhibits the highest fluorescence efficiency in methanol. © 2008 Elsevier Ltd. All rights reserved.