Witnessed by X-ray powder diffraction (XRD), Raman, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies, BiVO4 nanofibers and porous nanostructures were successfully fabricated by electrospinning method using NH4VO3 and Bi(NO3)(3) as starting materials. Polyvinylpyrrolidinone (PVP) was used to tune the viscosity and spinnability of the electrospinning sol. The slow decomposition and combustion of PVP matrix prevented rapid crystal growth of BiVO4 nanostructures leading to considerably small crystallite size (approximately 19.1-28.3 nm) with less surface defects after two hours calcination at varying temperatures. This paid great tributes to the superior visible light photocatalytic activity when compared to the submicron sized BiVO4 prepared in the absence of PVP. (C) 2015 Elsevier Ltd. All rights reserved.