BiVO4 nanofibers were sucossfully prepared by electrospinning and precisely controlled heat treatment. The obtained BiVO4 nanofibers showed an enhanced phofo, catalytic activity in the degradation, of rhodamine-B under visible light irradiatibm The as-prepared nanofibers were characterized by means of numerous techniques. The enhanced photocatalyst activity is attributed to the formation of a phase junction of tetragonal sheelite (s-t) and monodinic sheelite (s-m) phases in the electrospun BiVO4 nariofibersWe have also investigated the band 'structure of BiVO4 using, first principle calculation. The Main photon transition mechanism of the photocatalyst should be from the O 2p to V 3d state of s-m/t BiVO4,nanofibers.