Abstract: Novel TiO₂/BiVO₄ microfiber heterojunctions were constructed using cotton as biomorphic templates. The as-synthesized samples were characterized by scanning electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy, UV-Vis diffuse reflectance spectra and photocatalytic experiment. The morphology of the as-synthesized TiO₂/BiVO₄ composites was consisted of a large quantity of microfiber structures with diameter from 2.5 μm to 5 μm, and the surface of samples became more coarse and compact with the increase of weight ratio of TiO₂. The TiO₂/BiVO₄ samples with proper content (10.00wt%) showed the highest pho-tocatalytic degradation activity for methylene blue (MB) degradation among all the samples under visible light, and 88.58%MB could be degraded within 150 min. The enhancement of photocatalytic activity was mainly attributed to the formation of n-n heterojunction at the contact interface of TiO₂ and BiVO₄, which not only narrowed the band gap of BiVO₄ for extending the absorption range of visible light, but also promoted the transfer of charge carriers across interface. A possible photodegradation mechanism of MB in the presence of TiO₂/BiVO₄ microfibrous photocatalyst was proposed.