Molybdenum (Mo) doped BiVO₄ was fabricated via a simple electrospun method. Morphology, structure, chemical states and optical properties of the obtained catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), N₂ adsorption–desorption isotherms (BET) and photoluminescence spectrum (PL), respectively. The photocatalytic properties indicate that doping Mo into BiVO₄ can enhance the photocatalytic activity and dark adsorption ability. The photocatalytic test suggests that the 1% Mo-BiVO₄ shows the best photocatalytic activity, which is about three times higher than pure BiVO₄. Meanwhile, 3% Mo-BiVO₄ shows stronger dark adsorption than pure BiVO₄ and 1% Mo-BiVO₄. The enhancement in photocatalytic property should be ascribed to that BiVO₄ with small amount of Mo doping could efficiently separate the photogenerated carries and improve the electronic conductivity. The high concentration doping would lead the crystal structure transformation from monoclinic to tetragonal phase, as well as the formation of MoO₃ nanoparticles on the BiVO₄ surface, which could also act as recombination centers to decrease the photocatalytic activity.