(10Li(2)O-20GeO(2)-30ZnO-(40-x)Bi2O3-xFe(2)O(3) where x = 0.0, 3, 6, and 9 mol%) glasses were prepared. A number of studies, viz. density, differential thermal analysis, FT-IR spectra, DC and AC conductivities, and dielectric properties (constant epsilon', loss tan delta, AC conductivity, sigma (ac), over a wide range of frequency and temperature) of these glasses were carried out as a function of iron ion concentration. The analysis of the results indicate that, the density and molar volume decrease with an increasing of iron content indicates structural changes of the glass matrix. The glass transition temperature T (g) and onset of crystallization temperature T (x) increase with the variation of concentration of Fe2O3 referred to the growth in the network connectivity in this concentration range, while glass-forming ability parameter Delta T decrease with increase Fe2O3 content, indicates an increasing concentration of iron ions that take part in the network-modifying positions. The FT-IR spectra evidenced that the main structural units are BiO3, BiO6, ZnO4, GeO4, and GeO6. The structural changes observed by varying the Fe2O3 content in these glasses and evidenced by FTIR investigation suggest that the iron ions play a network modifier role in these glasses while Bi2O3, GeO2, and ZnO play the role of network formers. The temperature dependence of DC and AC conductivities at different frequencies was analyzed using Mott's small polaron hopping model and, the high temperature activation energies have been estimated and discussed. The dielectric constant and dielectric loss increased with increase in temperature and Fe2O3 content.