Electron paramagnetic resonance (EPR), DC conductivity and differential scanning calorimetry (DSC) of the xNiO (.) (0.3 - x)Li2O (.) 0.7B(2)O(3) (0.0 less than or equal to x less than or equal to 0.15) containing 1.0 and 2.0 mol% Of V2O5 have been studied. Spin Hamiltonian parameters, dipolar hyperfine coupling parameter, P, and Fermi contact interaction parameter, K, have been calculated. It is found that the size of the 3d(xy) orbit of unpaired electron in the vanadium ion is increased with NiO contents in the sample. The DC conductivity decreases with increase in the NiO:Li2O ratio. Characteristic glass transition temperature, T-g is found to increase with increase in NiO content. Theoretical optical basicity of the samples is also calculated.