EPR and optical absorption investigations are carried out at room temperature on vanadyl doped ARbB(4)O(7) (A = Li, Na, K) glasses. These results indicate that the VO2+ ion enters the glass matrix into a tetragonally compressed octahedral site. The spin-Hamiltonian parameters calculated from the EPR spectra for the three glass systems LRB, NRB and KRB are: g(parallel to) = 1.948, g(perpendicular to) = 1.976, A(parallel to) = 157 x 10(-4), A(parallel to) = 58 x 10(-4) cm(-1); g(parallel to) = 1.948, g perpendicular to = 1.977, A(parallel to) = 157 x 10(-4), A perpendicular to = 58 x 10(-4) cm(-1) and g(parallel to) = 1.948, g(parallel to) = 1.979, A(parallel to) = 157 x 10(-4), A(perpendicular to) = 59 x 10(-4) cm(-1), respectively. The optical spectrum exhibits three characteristic bands for all these glasses suggesting C-4v symmetry. The crystal field and tetragonal field parameters evaluated using the optical data for the three systems LRB, NRB and KRB are: Dq = 1666, Ds = -3339, Dt = 450 cm(-1); Dq = 1666, Ds = -3329, Dt = 441 cm(-1) and Dq = 1666, Ds = -3219 and Dt = 507 cm(-1), respectively. The bonding parameters indicate a moderately covalent bond between the metal ions and ligands. (C) 2007 Elsevier B.V. All rights reserved.