With doping a bit of phosphorus (P) into the lattice of FeVO nanobelts, FePVO solid solution nanobelts have been successfully synthesized for the first time via a simple electrospinning process. The as-prepared products were characterized by thermogravimetric and differential scanning calorimetry (TG-DSC), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-vis absorbance spectroscopy, and electrochemical impedance spectra (EIS). The results demonstrated that the lattice constants of FeVO were changed and transport of charge carriers was improved after doping P element. Furthermore, the FePVO nanobelts presented an admirable one-dimensional morphology and the excellent photocatalytic properties for the degradation of methylene blue (MB) solution under the visible light irradiation.