Spectroscopic investigations of V2O5 doped ZnO–Sb2O3–B2O3glass system was prepared by melt-quenching technique. ZnO–Sb2O3–B2O3 glasses containing varying concentrations of V2O5 ranging from 0.1 to 1.0 mol% were prepared, here spectroscopic studies such as Optical absorption, IR and ESR spectra have been carried out as a function of vanadium ion concentration. The optical absorption spectrum of glasses has exhibited two broad absorption bands corresponding to 2B2→2B1 and 2B2→2E transitions of VO2+ ions. The appearances of vibration bands in IR spectra are characteristic for B-O-B and V-O-V linkages, showing the network former role of V2O5. Vanadium ions are believed to be present in two possible valence states, namely V4+and V5+. Here with increasing presence of V2 O5 in the glass network, vanadium ions mostly exist in V4+state and occupy modifying positions. Such increase obviously suggests most structural disorder in the network as the concentration of V2 O5 is increased.