Controlled WO3 morphologies, such as nanorods and octahedral structures, were synthesized by the hydrothermal technique using sulfate salts based structure directing agents (SDAs). The role of the sulfate salts' cation in controlling the shape, size and phase of WO3 nanomaterials was investigated by choosing sulfate salts whose cations are from d-bloc elements (FeSO4, (NH4)(2)Fe(SO4)(2), CoSO4, CuSO4, ZnSO4), an alkaline earth metal (MgSO4) and a non-metal ((NH4)(2)SO4). In addition chloride (MnCl2) and acetate (Zn(CH3CO2)(2)) anion based SDAs were also used in order to clarify the role of sulfate ions in the growth of WO3 nanostructures. We controlled the pH of the reaction medium with oxalic acid. The obtained WO3 samples were investigated by SEM, micro-Raman, and XRD. At pH = 1, the WO3 samples exhibit novel superstructures consisting of aligned hexagonal nanorods, whereas at pH = 5.25, novel twin octahedral morphology with a cubic structure is obtained. The results demonstrate that the phase and morphology change is influenced by the pH and both the anion and the cation of the SDA. A growth mechanism for the obtained novel WO3 morphologies is presented. (C) 2012 Elsevier B.V. All rights reserved.