Three new copper(I) coordination polymers [Cu2(µ-L)(µ-I)2)(PPh3)2]n (1), [Cu2(µ-L) (µ-Br)2(PPh3)2]n (2) and [Cu2(µ-L)(µ-Cl)2(PPh3)2.CH3CN]n (3) have been synthesized by reactions of CuX (X=I, Br and Cl) with PPh3 and the polydentate azino-pyridyl ligand L. These complexes have been characterized by elemental analyses, IR, UV–Vis and NMR spectroscopy. The crystal structures of the complexes 1 and 3 have been determined by single-crystal X-ray analysis and it has been found that these are 1-D co-ordination polymers containing bridged halide ions as well as the azino-pyridyl ligand L. Matching of X-ray powder patterns and theoretical studies reveal that the complex 2 is also a 1-D co-ordination polymer. The ligand L is non-emissive at room temperature in dichloromethane, whereas the complexes 1, 2 and 3 are photoluminescent. The E1/2 values of the CuI-CuII couple for 1, 2 and 3 are within 0.75–0.80 (vs. Ag/AgCl in 1M KCl, scan rate 100mVs−1. DFT and Hirshfeld surface studies have also been performed for 1, 2 and 3.