Ultra-thin W(18)O(49) nanowires were initially obtained by a simple solvothermal method using tungsten chloride and cyclohexanol as precursors. Thermal processing of the resulting bundled nanowires has been carried out in air in a tube furnace. The morphology and phase transformation behavior of the as-synthesized nanowires as a function of annealing temperature have been characterized by x-ray diffraction and electron microscopy. The nanostructured bundles underwent a series of morphological evolution with increased annealing temperature, becoming straighter, larger in diameter, and smaller in aspect ratio, eventually becoming irregular particles with size up to 5 µm. At 500 °C, the monoclinic W(18)O(49) was completely transformed to monoclinic WO(3) phase, which remains stable at high processing temperature. After thermal processing at 400 °C and 450 °C, the specific surface areas of the resulting nanowires dropped to 110 m(2) g(-1) and 66 m(2) g(-1) respectively, compared with that of 151 m(2) g(-1) for the as-prepared sample. This study may shed light on the understanding of the geometrical and structural evolution occurring in nanowires whose working environment may involve severe temperature variations.