The study investigates the influence of praseodymium (Pr) doping on bismuth ferrite (BiFeO3/BFO) nanofibers and their structural, morphological, magnetic, optical, and photocatalytic properties. A series of bismuth ferrite nanofibers with varying concentration of Pr (Bi1-xPrxFeO3, x = 0.00, 0.05, 0.10, and 0.15 mol%) were successfully synthesized using an electrospinning technique. XRD patterns revealed that structural transformation occurred from rhombohedral to orthorhombic upon effective doping of Pr3+ into BFO nanofibers. The X-ray photoelectron spectroscopy analysis confirmed that Bi, Fe, and O maintained their native oxidation states of +3 and -2, respectively in the bare and doped systems. Furthermore, the optical band gap value was significantly reduced from 2.35 to 2.22 eV as well as the recombination rates of charge carriers in the doped systems, especially in BP0.15O system. The photocatalytic performance of the prepared samples was studied by measuring the decomposition of rhodamine B (RhB) under sunlight irradiation. Outcomes showed that the doped-BFO nanofibers exhibited enhanced photocatalytic performance compared to pure BFO, with the BP0.15O system showing the 98 % degradation in 60 min. This enhancement could be attributed to the presence of Pr-energy levels, which facilitating enhanced separation, and charge transfer to the surface for the effective redox reactions.