Decoration of α-FeOOH nanorods over PAN nanofibers was performed using the electrospinning technique. The as-designed decorated nanofibers were characterized using various techniques such as wide-angle powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared (FTIR) spectroscopy, UV-vis spectrophotometry (UV-vis), thermogravimetry analysis (TGA), N2 adsorption-desorption isotherm (BET), and X-ray photoelectron spectrometry (XPS). α-FeOOH NRs were decorated uniformly over PAN fibers, as observed from its morphological investigation, which shows novelty. 1D α-FeOOH nanorods with PAN nanofibers have not been studied for photocatalytic characteristics. No literature mentions that α-FeOOH nanorods coated in PAN NFs act as photocatalysts to degrade hazardous azo dyes. α-FeOOH nanorods on PAN NFs inhibit aggregation and increase dye binding, boosting photocatalytic performance. PAN/α-FeOOH NFs have a maximal specific surface area with a reduced bandgap than α-FeOOH NRs. PAN/α-FeOOH nanofibers showed excellent photocatalytic activity for the degradation of Trypan blue (TB) (120 min, 99.7%) and Eriochrome black T (EBT) dyes (160 min, 97.6%), respectively, under solar light irradiation. PAN/α-FeOOH NFs have the potential to be used in the degradation of azo dyes and the treatment of wastewater due to their low energy requirements and versatility.