Bi(VO4)(1-m)(PO4)(m) nanofibers were prepared by effective structural doping through an electrospinning method with subsequent calcination. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), UV-vis absorbance spectroscopy, electrochemical impedance spectra (EIS), Mott-Schottky analysis, and photoluminescence (PL) spectroscopy. The diameter of the as-prepared fibers was about 200-400 nm. We found that the 0.5% P(molar ratio)-doped BiVO4 samples exhibited better photocatalytic activity for methylene blue (MB) than monoclinic BiVO4.