WO3 center dot 0.33H(2)O networks were prepared by using structure-directing agent under a hydrothermal condition. The influences of the valence state (Na+, Ca2+), radius of ions (Ca2+ < Sr2+ < Ba2+), molar ratio of W to Ca, and reaction time on the crystal structure and morphology of the products have been investigated systematically. It was found that higher ion valence state (2 +), smaller ion radius (Ca2+), 1:1 molar ratio of W to Ca and 15 h reaction time at 180 degrees C were the optimal experimental condition for the growth of well-defined three- dimensional networks. The proposed growth mechanism of the nanostructures can provide important information for structure design and morphology-controlled synthesis of WO3 center dot 0.33H(2)O and other oxides. (c) 2012 Elsevier B.V. All rights reserved.