Selected glasses of Fe(2)O(3)-PbO(2)-Bi(2)O(3) system have been transformed into nanomaterials by annealing at temperature close to crystallization temperature (T(c)) for 1 h. The effects of the annealing of the present samples on its structural and electrical properties were studied by Mossbauer spectroscopy, transmission electron micrograph (TEM), differential scanning calorimeter (DSC) and dc conductivity (sigma). Mossbauer spectroscopy was used in order to determine the states of iron and its hyperfine structure. The effect of nanocrystalization on the Mossbauer hyperfine parameters did not exhibit significant modifications in present glasses. However, in case of glass ceramic nanocrystals show a distinct decrease in the quadrupole splitting (Delta) is observed, reflecting an evident decrease in the distortion of structural units like FeO(4) units. In general, the Mossbauer parameters of the nanocrystalline phase exhibit tendency to increase with PbO(2) content. TEM of as-quenched glasses confirm the homogeneous and essentially featureless morphology. TEM of the corresponding glass ceramic nanocrystals indicates nanocrystals embedded in the glassy matrix with average particle size of about 32 nm. The crystallization temperature (T(c)) was observed to decrease with PbO(2) content. The glass ceramic nanocrystals obtained by annealing at T(c) exhibit improvement of electrical conductivity up to four orders of magnitude than the starting glasses. This considerable improvement of electrical conductivity after nanocrystallization is attributed to formation of defective, well-conducting phases "easy conduction paths" along the glass-crystallites interfaces. (C) 2010 Elsevier Ltd. All rights reserved.