xTeO(2) + (70 - x)B2O3 + 5TiO(2) + 24R(2)O:1CuO (x = 10, 35 and 60 mol%; R = Li, Na and K) glass system were studied by spectroscopic techniques such as ESR, optical absorption, Raman and IR. From ESR spectra, the spin Hamiltonian parameter values indicate that the ground state of Cu2+ is d(x2-y2) and the site symmetry around the Cu2+ ion is tetragonally distorted octahedral coordination. Bonding parameters calculated from optical absorption and ESR data are found to change with alkali oxide and TeO2 content. Bonding parameters indicate a slight covalency for the in-plane sigma bonding as compared to in-plane and out-of-plane pi bonds. Both Raman and IR results show that glass network consists of TeO3, TeO4, BO3, BO4 and RiO(4) group as basic structural groups. BO3-BO4- ring structure interconnected by TeO3- and TeO4- groups, where the BO4- groups are neighbors of the TeO3- groups. BO3 -> BO4 transition is also observed, which correlates with the transition of TeO4 -> TeO3 via TeO3+1. (C) 2011 Elsevier Ltd. All rights reserved.