The Cu(II) complexes with hetarylformazanes (HF) formed in solutions, polycrystals, and AN-18 polymeric ionite modified with HF were studied by EPR method and were found to have almost identical structures. The configuration of the Cu2+ coordination surrounding (square-planar or pseudotetrahedral) is specified by the substituents at N1 in formazane fragments. Complexes with coordination unit Cu(4N) were formed mainly, when the ligands were taken in excess, while in the case of the ligand deficiency and with the coordinating OH group in benzene ring, the complexes with the Cu(3NO) coordination unit were formed. The covalence of in-plane metal-ligand σ-bond was found to be affected by the substituents. The formation of binuclear copper complexes in solutions and polycrystals was established in the case of deficiency of the ligand with SO3H substituent in benzene ring.