Glasses having the composition xCoO.(0·30-x)M 2 O.0·70B 2 O 3 (M=Li, K) have been prepared over the range 0·00≤x≤0·15 containing 1·0 and 2·0 mol% of V 2 O 5 . Spin-Hamiltonian parameters, dipolar hyperfine coupling parameter, P, and Fermi contact interaction term, K, of the VO 2+ ions have been calculated. It is found the V 4+ ions in these glasses exist as VO 2+ in octahedral coordination with a tetragonal distortion. Results suggest that hyperfine spectra on vanadium are not observed when the amount of CoO exceeds a certain value, which depends on the type of alkali and the amount of V 2 O 5 . The 3dxy orbital in the vanadium ion expands and the tetragonal distortion around vanadium ion increases with the increase in the COO.M 2 O ratio. There is virtually no change in the microscopic structure around vanadium due to annealing or when Li 2 O is replaced by K 2 O. The d.c. conductivity decreases when Li 2 O is replaced by K 2 O, keeping the concentration ofCoO and B 2 O 3 constant. Addition of CoO to the sample shows a "blocking effect" on the overall mobility of alkali ions. As a result the conductivity of the sample decreases with increase in COO:M 2 O ratio.