The relationship among the composition, structure and selected properties for five series of silver phosphate glasses containing 0, 5, 10, 15 and 20wt% Fe$_2$O$_3$ has been investigated. The synthesized glasses have been characterized using different experimental techniques. X-ray diffraction studies revealed that the glasses are amorphous in nature. IR spectral studies have shown the presence of characteristic P–O–P linkages of linear phosphate chains,presence of O–P–O units in the phosphate tetrahedral and the formation of P–O–Fe bonds in the doped glass. It is also confirmed that due to doping of Fe$_2$O$_3$, loosening of glassy structure occurred and the glass became more disordered. Differential scanning calorimetric (DSC) studies revealed that glass transition temperature increased with Fe$_2$O$_3$ concentration. Scanning electron microscopic studies have shown that Fe$_2$O$_3$ doping modifies the microstructures of the glass and at lower concentration of dopant, a nanostructure is obtained. Electrical conductivity measurements from 303 to 373 K in a frequency range from 100 Hz to 5 MHz have indicated that all glasses are ionic conductors with Ag$^+$ ions as the charge carrier. Fe$_2$O$_3$ doping in silver phosphate glass increased the electrical conductivities. Results have shown that dielectric constants increased with the increase of temperature at all the frequencies; a.c. and d.c. conductivities have been separated and a Cole–Cole plot is also drawn. Dielectric losses in all the glasses decreased with frequency at a particular temperature. It is found that Ag$_2$O–P$_2$O$_5$ glass doped with 5wt% Fe$_2$O$_3$ gives high OCV value and the doped glass can be used as an electrolyte for solid-state batteries.