The effect of varying iron content on the crystallization behavior and electrical conductivity mechanism of glass nanocomposite based on the system xFe ⋅ (1‐x) ⋅ (0.3 V2O5 ⋅ 0.2MoO3 ⋅ 0.4CdO ⋅ 0.1ZnO) (x=0.0, 0.05 and 0.1) was investigated by differential scanning calorimetry (DSC), Fourier transforms infrared (FTIR), X‐ray diffraction (XRD), and field emission‐scanning electron microscopy (FESEM). Different crystal phases and the average size of the developed nanocrystallites in the as‐prepared samples have been obtained from the XRD diffraction data. The size of estimated nanocrystallites increases up to Fe (x) content 0.05, after which the size of nanocrystallites decreases as the Fe content in the compositions increases. FESEM micrographs confirm the formation of plate‐like and dendrite nano crystallites throughout the glass matrix. Energy‐dispersive X‐ray spectroscopy (EDX) mapping analysis shows the weight percentage of each constituent element. The dc activation energy (Eσ), as well as activation energy (EH) for hopping frequency of as‐prepared samples, gradually decreases with increasing Fe content whereas AC and DC conductivity gradually increased.