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Glass ceramics with composition 10Na2O− 30PbO−10Bi2O3−(50-x)SiO2: xV2O5 (0 ≤ x ≤ 5) were synthesized by melt quenching and heat treatment method. XRD and SEM studies have indicated that the samples contain well defined and randomly distributed grains of different crystalline phases. Optical absorption spectra of these samples exhibited two absorption bands at 629 and 835 nm which are the characteristics of V4+ ions. The EPR spectra of these samples have exhibited well resolved hyperfine structure consisting of sixteen-eight parallel and eight perpendicular lines with a raise in their intensity with an increase in the content of V2O5 up to 3 mol% indicates the increase of redox ratio V4+/V5+ in the glass ceramic matrix. [ABSTRACT FROM AUTHOR]