Vanadate glasses have numerous industrial applications and enhancement of their electrical conductivity is of interest for conducting glass for electronic and optical devices. The effect of substitutional doping of SnIV (4d10) for FeIII on the local structure and electrical conductivity (σ) of barium iron vanadate glass is investigated in this study. The σ value of as‐cast 20BaO · 3SnO2 · 7Fe2O3 · 70V2O5 glass (5.9 × 10−7 S cm−1) is comparable to that of as‐cast 20BaO · 10Fe2O3 · 70V2O5 glass. The σ value of the doped glass increases to 1.9 × 10−1 S cm−1 after isothermal annealing at 500 °C for 15 min, which is an order of magnitude larger than that of the undoped glass annealed under the same conditions. From room‐temperature Mössbauer spectra of conductive vanadate glasses annealed at 500 °C for 15 min, it is demonstrated that the quadrupole splitting of the FeIII (0.60 mm s−1) in 3 mol%‐SnO2 containing vanadate glass is slightly smaller than that of SnO2‐free vanadate glass (0.65 mm s−1). This indicates smaller distortion of FeO4 and VO4 tetrahedra in the SnO2‐containing glass compared to the undoped glass, which is responsible for a marked increase in the carrier mobility.