A facile and rapid microwave irradiation method was explored for the synthesis of bismuth phosphate (BiPO4) nanostructures with various morphologies and phases in different solvents. The BiPO4 products were characterized by powder X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflection spectroscopy (DRS). The effect of the solvents on the formation of the BiPO4 nanostructures was discussed on the basis of experimental results. The different BiPO4 nanostructures exhibited different optical properties, BET surface areas and photocatalytic activities on the degradation of methyl orange (MO) under UV and visible light irradiation. The experimental results suggested that the photocatalytic activity was closely relative with the crystalline phase and band gap of BiPO4. Hexagonal BiPO4 nanoparticles with narrow band gap showed the highest photocatalytic performance. (C) 2011 Elsevier Inc. All rights reserved.