Despite multiple reports and investigations performed on dipicolinate compounds, great attention to their further study is still being paid, because of their structural variability, interesting properties and applications in many fields such as material chemistry, medicine and bioinorganic chemistry [1, 2]. Compounds of copper(II) containing nicotinamide or its derivatives as N-donor ligands have been chosen considering that they could be involved into the hydrogen-bond networks through the carboxamide group [3] and thus are suitable candidates for construction of supramolecular architectures and together with dipicolinate ligand, which can bind to a metal centre in a variety of coordination modes [4, 5], are of interest from a supramolecular chemistry point of view. Therefore using the above-mentioned ligands four copper(II) dipicolinate complexes have been synthesized, namely {[Cu(pca)(dipic)(H2O)]·H2O} (1), [Cu(nia)(dipic)(H2O)] (2), {[Cu(mnia)(dipic)(H2O)]·2H2O} (3) and {[Cu(inia)(dipic)]n·2CH3OH} (4) (dipic = anion derived from pyridine-2,6-dicarboxylic acid also well-known as dipicolinic acid, pca = pyrazinecarboxamide, nia = nicotinamide, mnia = N-methylnicotinamide and inia = isonicotinamide). Crystal structures of all the compounds have been determined, supramolecular contacts such as hydrogen bonding described and all prepared compounds have been also studied by EPR spectroscopy. The X-ray diffraction analysis revealed that all of the copper(II) complexes are of distorted square-pyramidal geometry with five-coordinated central copper(II) atoms through one nitrogen donor atom of nicotinamide or its derivatives, one nitrogen donor atom and two oxygen donor atoms of a tridentate chelating dipicolinate anion and one oxygen donor atom from coordinated water molecule (besides complex (4)). In the complex 4 anion of dipicolinic acid has one carbonyl oxygen atom of carboxylate group acting as bridging to the neighbouring copper(II) atom, what resulted into the formation of polymeric compound. The complex molecules to each other and solvent molecules in the cases, where uncoordinated solvent molecules (water or methanol) are located in the crystal structure, are linked together through complicated hydrogen-bond networks in all cases and form either 2D or 3D supramolecular frameworks. The X-band EPR spectra of all prepared copper(II) complexes were recorded at room, as well as at low temperature 98 K. The g-factor relation g// > g┴ > 2.0023 confirmed the dx2-y2 ground electronic state.