Reaction of bipyridylamide ligands N-(3-pyridyl)nicotinamide (3-pna), N-(4-pyridyl)nicotinamide (4-pna) and N-(4-pyridyl)isonicotinamide (4-pina) with Cu(I) salts afforded four coordination polymers. X-ray crystallography analysis showed one-, two- and three-dimensional networks. The correlation between the pyridyl nitrogen donor disposition and dimensionality of the structures was discussed. Reflectance UV–Vis and fluorescence spectroscopic methods were used to characterize the MLCT features of these complexes. Thermal stability of the coordination polymers under nitrogen was also investigated.