To study the impact of iron oxide on the structural and photochromic properties of some alumino-borate glasses, a glass system 75% B2O3 + 5% Al2O3 + (20-y) % Na2O + y % Fe2O3; where y = 4, 2, and 0 was synthesized by melt-quenching technique. The amorphous nature of the prepared glass system was confirmed by X-ray diffraction (XRD) analysis. The existence and values of ratios of some structural groups such as; BO3 and BO4, were investigated by using Fourier transform infrared spectroscopy (FTIR). Traditional techniques and standard formulas were used to determine the experimental density (ρexp), empirical density (ρemp) and molar volume (Vm). The photochromic properties in terms of transmittance were employed to study the impact of sunlight on the optical properties. The ρemp, ρexp and Vm values of the investigated glasses showed increasing behaviors, whereas the optical band gap (Eg) showed an opposite behavior. Moreover, anomalous behavior for transmittance was obtained; increment with irradiation. These obtained results nominate these iron-borate glasses for potential and promising applications such as optoelectronic devices and solar cells.