The structural and physical properties ofxFe2O3-(40-x)B2O3-60V2O5 (0≤x≤20)glass system have been investigated. The samples were prepared by normal melt-quench technique. The structural changes were inferred by means of FTIR by monitoring the infrared (IR) spectra in the spectral range 600–4000cm-1. The absence of boroxol ring (806 cm-1) in the present glass system suggested that these glasses consist of randomly connectedBO3andBO4units. The conversion ofBO3toBO4andVO5toVO4tetrahedra along with the formation of non-bridging oxygen's (NBOs) attached to boron and vanadium takes place in the glasses under investigation. The density and molar volume of the present glass system were found to depend onFe2O3content. DC conductivity of the glass system has been determined in the temperature range 310–500 K. It was found that the general behavior of electrical conductivity was similar for all glass compositions and found to increase with increasing iron content. The parameters such as activation energy, average separation between transition metal ions (TMIs), polaron radius, and so forth have been calculated in adiabatic region and are found consistent with Mott's model of phonon-assisted polaronic hopping.