One-dimensional Bi2MoxW1-xO6 (x = 0, 0.2, 0.5, 0.67, and 1) photocatalysts have been successfully synthesized for the first time by a straightforward electrospinning technique with a calcination process. The as-formed Bi2MoxW1-xO6 nanofibers are composed of inter-linked nanosheets of 30-50 nm in size and characterized by thermogravimetric and differential scanning calorimetric, Fourier transform infrared, Raman spectra, X-ray powder diffraction, scanning electron microscope, Brunauer-Emmett-Teller, transmission electron microscope, UV-Vis spectroscopy, photoluminescence, HPLC, and EIS. The photodegradation behaviors towards organic dyes, including rhodamine B (RhB) and methylene blue (MB) are investigated, and the results illustrate that Bi2MoxW1-xO6 nanofibers exhibit the highest photocatalytic performance under visible light irradiation than Bi2MoxW1-xO6 (x=0, 0.2, 0.5, 0.67, and 1) samples. The possible mechanisms of the enhanced photocatalytic properties are discussed in detail.