Bismuth phosphate (BiPO4) nanofibers were prepared through a simple electrospinning method and followed by calcination treatment. The prepared samples were characterized with thermogravimeter and differential scanning calorimeter (TG-DSC), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N-2 adsorption-desorption measurements, UV-vis absorbance spectroscopy, electrochemical impedance spectra (EIS), and the photoluminescence spectra. The diameter of the as-prepared fibers is about 200 run. The nanofibers are mesoporous and composed of the linked nanoparticles with sizes of about 15 run. The rate constant of degradation of APMP pulping effluent for mesoporous nanofibers is 1.55 times of that of the powders prepared by sol-gel method and 3.72 times of that of P25.