The glasses with the composition xBaO-(30-x) TeO2-10TiO2-58B2O3-V2O5/CuO with x=10,15,20,25 mole% were prepared by melt quenching method. Cu2+ and VO2+ ions were used as the spin probes. X-ray diffraction studies revealed the amorphous nature of the glasses. From the EPR spectra the spin-Hamiltonian parameters were evaluated. Number of spins participating in the resonance and paramagnetic susceptibility values were evaluated. From the spin-Hamiltonian parameters of VO2+, it was observed that the vanadyl ions exist as VO2+ ions in octahedral coordination with tetragonal compression and have C4V symmetry with ground state dxy. The spin-Hamiltonian parameter values in the case of Cu2+ indicated that the ground state of Cu2+ was dx2-y2 orbital (2B1g) and the site symmetry around Cu2+ is tetragonally distorted octahedral. From the EPR and optical data the bond parameters were evaluated.