The influence of adding Fe₂O₃ at the expense of Na₂O in sodium lead borate glasses on the structural, physical and electrical properties have been investigated. Results obtained from Fourier transform infrared (FTIR) spectra indicated that Fe₂O₃ plays an important role in converting three coordinated boron atoms [BO₃] to four coordinated boron atoms [BO₄]. The physical properties such as density and molar volume helped to evaluate the compact structure of the prepared glass samples due to presence of [BO₄] groups. The increase of Fe₂O₃/Na₂O replacements led to increasing the microhardness values and decreasing the thermal expansion coefficients of the studied glasses. The increase of Fe₂O₃/Na₂O replacements generally decreased the AC conductivity. That decrease might be due to converting of the three coordinated boron atoms [BO₃] to four coordinated boron atoms [BO₄]. Dielectric constants of the samples might be an indication of the distortion in the coordinated boron atoms. The obtained experimental data indicated the internal structure of glass network and the change of the structure of the samples from three [BO₃] to four coordinated boron atoms [BO₄].