Nanoparticles of bismuth layered Aurivillius phase, Bi2W2O9, have been synthesized by annealing of precursor prepared by high energy milling in ball mill. The obtained powders have been investigated using the XRD, TEM, SEM, diffuse reflectivity, Raman and infrared spectroscopy. The results show that mechanochemical activation allows obtaining Bi2W2O9 at much lower temperatures than those required in a conventional solid state reaction or synthesis through a complex organic precursor. As a result, material with smaller grain size can be obtained. Therefore this synthesis method is the best route to enhance photocatalytic activity of Bi2W2O9. Our results also show that milling time has great impact on the crystallization mechanism. Bi2W2O9 crystallizes easily already at 600 degrees C from precursor milled by 8 h. However, prolong milling time results in stabilization of an unknown phase or phases, which crystallize below 700 degrees C, and transform into the well-known Bi2W2O9 phase after annealing at 750 degrees C. (c) 2010 Elsevier BM. All rights reserved.