Bismuth ferrite has become an effective semiconductor photocatalyst for the degradation of various wastewaters due to its narrow band gap, high chemical stability, and good visible light response. Pure phase BiFeO3 nanofibers were prepared by electrospinning method. The optimal degradation conditions for Congo Red were obtained through single factor experiments such as calcination temperature, PVP concentration, collection distance, spinning voltage, and pushing speed. Four factors that significantly affect photocatalytic efficiency were selected for response surface analysis experiments with four factors and three levels. After optimization, the optimal PVP concentration was 12.17 wt%, collection distance was 14.07 cm, and spinning voltage was 12.03 kV The pushing speed is 0.74 um·s-1, and under this condition, the efficiency of BiFeO3 photocatalytic degradation of Congo red can reach 90.43%. The phase analysis and morphology characterization of bismuth ferrite nanofibers were carried out using X-ray diffraction, scanning electron microscopy, Raman spectroscopy, and Fourier transform infrared spectroscopy. The results showed that the pure phase BFO nanofibers prepared by electrospinning had a rough surface and obvious particle sensation, presenting a one-dimensional rod-shaped structure with a size of about 300 nm. This nanorod-shaped structure has a larger specific surface area and more active sites, Can improve the photocatalytic degradation efficiency of BFO.