One-dimensional Bi 2 MoO 6 nanotubes were successfully synthesized by the electrospinning technique in combination with the calcination process. The as-prepared samples were characterized by thermogravimetric and differential scanning calorimetry, Fourier transform-infrared spectroscope, microscopic Raman spectrometer, X-ray diffraction, scanning electron microscope, and transmission electron microscope. The hollow morphology of the Bi 2 MoO 6 nanotubes can be obtained after calcining the electrospun gel nanofibers. The results of the photocatalytic degradation tests show that the Bi 2 MoO 6 nanotubes possessed a much higher degradation rate of methylene blue than that of degussa P25. In particular, Bi 2 MoO 6 nanotubes calcined at 600 °C for 2 h (marked as BMO-600) exhibited much higher photocatalytic activity than that of γ-Bi 2 MoO 6 phase calcined at 500 °C for 2 h (BMO-500) and that of γ′-Bi 2 MoO 6 phase calcined at 700 °C for 2 h (BMO-700) under simulated sunlight irradiation. The formation of the surface-phase junctions between low-temperature γ-Bi 2 MoO 6 phase and high-temperature γ′-Bi 2 MoO 6 phase may be responsible for the highest photocatalytic activity of the BMO-600 sample.