Single-crystalline non-stoichiometric tungsten oxide nanowires were initially prepared using a simple solvothermal method. High resolution transmission electron microscopy (HRTEM) investigations indicate that the tungsten oxide nanowires exhibit various crystal defects, including stacking faults, dislocations, and vacancies. A possible defect-induced mechanism was proposed to account for the temperature-dependent morphological evolution of the tungsten oxide nanowires under thermal processing. Due to the high specific surface areas and non-stoichiometric crystal structure, the original tungsten oxide nanowires were highly sensitive to ppm level ethanol at room temperature. Thermal treatment under dry air condition was found to deteriorate the selectivity of room-temperature tungsten oxide sensors, and 400 degrees C may be considered as the top temperature limit in sensor applications for the solvothermally-prepared nanowires. The photoluminescence (PL) characteristics of tungsten oxide nanowires were also strongly influenced by thermal treatment. (C) 2010 Elsevier Ltd. All rights reserved.