A relationship between physical properties and local structure of 20Li2O·10Fe2O3·xWO3·(70–x)V2O5 glass, abbreviated as xLFWV glass (x = 0 − 25 in mol%), was investigated by 57Fe-Mössbauer spectroscopy, Fourier transform infrared spectroscopy (FT-IR), differential thermal analysis (DTA), leaching test using 20 vol% HCl and DC two- or four-probe method. 57Fe-Mössbauer spectra of xLFWV glass showed an increase of quadrupole splitting (Δ) from 0.67 to 0.73±0.02 mm s − 1 and a constant isomer shift (δ) of 0.39±0.01 mm s − 1 with an increase of ‘x’ from 0 to 25. This suggests that FeIIIO4 tetrahedra gradually increase their local distortion along with a substitution of WO3 for V2O5. DTA of xLFWV glass showed an increase in glass transition temperature (Tg) from 252 to 298