Abstract: In this work, a rapid step sintering technique combining sol-gel and electrospinning was proposed for the preparation of the nanofibers based on single-crystal BiFeO₃. The structure and morphology of the prepared nanofibers were thoroughly characterized by thermogravimetric differential thermal analysis (TG-DTG), XRD, SEM, TEM, EDS, UV visible diffuse reflectance spectroscopy, and nitrogen adsorption-desorption assays. Subsequently, the photocatalytic performance for reducing Cr(VI) using the prepared nanofibers under visible light was investigated. On the strength of the larger specific surface area, nanofibers demonstrate higher photocatalytic activity compared to the nanoparticles prepared by the conventional sol-gel method. The hole-depleting agent, tartaric acid, promotes the occurrence of photocatalytic reduction of Cr(VI) reaction, resulting in an 87% increase in the reduction efficiency. In conclusion, the prepared BiFeO₃ photocatalyst can respond to visible light and possess weak magnetic properties that make it capable of being recovered by magnetic fields, demonstrating promising prospect in the field of environmental purification.