Transparent crystalline tungsten oxide nanorod arrays for use as an electrochromic layer have been directly prepared on fluorine-doped tin oxide-coated glass via a facile tungsten film-assisted hydrothermal process using aqueous tungsten hexachloride solution. X-ray diffraction analysis and field-emission scanning electron microscopy were used to characterize the phase and morphology of the grown nanostructures. Arrays of tungsten oxide nanorods with diameter of ∼22 nm and length of ∼240 nm were obtained at 200°C after 8 h of hydrothermal reaction. We propose a growth mechanism for the deposition of the monoclinic tungsten oxide phase in the hydrothermal environment. The tungsten film was first oxidized to tungsten oxide to provide seed sites for crystal growth and address the poor connection between the growing tungsten oxide and substrate. Aligned tungsten oxide nanorod arrays can be grown by a W thin film-assisted heterogeneous nucleation process with NaCl as a structure-directing agent. The fabricated electrochromic device demonstrated optical modulation (coloration/bleaching) at 632.8 nm of ∼41.2% after applying a low voltage of 0.1 V for 10 s, indicating the potential of such nanorod array films for use in energy-saving smart windows.