Melt quenched "SnO 2 (50−x)PbO:50V 2 O 5 " glass system containing x = 5, 10, 15 in molar ratio has been investigated. Effects of heating rate, glass transition, crystallization, melting temperature and infrared spectra of SnO 2 substituted PbO-V 2 O 5 glass system are reported. XRD results show that perfect vitrification has been achieved for all the glass samples after annealing at 150˚C. DSC results have indicated that eutectic composition of the lead metavanadate has been maintained for all the glass systems up to 15 mole% of substitution. IR spectra for a SnO 2 substitution of 5 mole% V=O stretching frequency occur at 966 cm −1 without appearance of any additional peak. But for 10 mole% and 15 mole% SnO 2 substituted samples, additional peaks appear at 1023 and 1005 cm −1 indicating the effect of SnO 2 in the vanadate crystalline matrix such that there is an elongation of V=O bond. Since the crystalline matrix is affected, we can expect similar effect in the glass matrix also.