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Bismuth vanadate (BiVO4) is considered a potentially attractive candidate for the visible-light-driven photodegradation of organic pollutants. In an effort to enhance their photocatalytic activities, BiVO4 nanofibers with controlled microstructures, grain sizes, and crystallinities are successfully prepared by electrospinning followed by a precisely controlled heat treatment. The structural features, morphologies, and photo-absorption performances of the asprepared samples are systematically investigated and can be readily controlled by varying the calcination temperature. From the physicochemical analysis results of the synthesized nanofiber, it is found that the nanofiber calcines at a lower temperature, shows a smaller crystallite size, and lower crystallinity. The photocatalytic degradation of rhodamine-B (RhB) reveals that the photocatalytic activity of the BiVO4 nanofibers can be improved by a thermal treatment at a relatively low temperature because of the optimization of the conflicting characteristics, crystallinity, crystallite size, and microstructure. The photocatalytic activity of the nanofiber calcined at 350oC for the degradation of RhB under visible-light irradiation exhibits a greater photocatalytic activity than the nanofibers synthesized at 400oC and 450oC.