Bismuth vanadate (BiVO4) nanofibrous arrays were synthesized by a hydrothermal route. Fibrous structure with the average diameter of 100 nm and length of up to several micrometers was fabricated by the hydrothermal process at 160 degrees C for 48 h under the assistance of a cationic surfactant, cetyltrimethylammonium bromide (CTAB). The BiVO4 nanofibers possessed well-crystallized monoclinic scheelite structure.