Ultrafine one-dimensional WO3 nanorods (NRs) with diameters of 10-200 nm have been fabricated using a hydrothermal synthesis method. The optical performance of the WO3 NRs strongly depends on their various defects as well as their crystal quality. Upon exposure to trace quantities of ethanol gas, the photoluminescence (PL) spectra of these nanorod samples under ultraviolet illumination showed a large variation in intensity. WO3-NR-based ethanol gas sensing via PL spectra variation demonstrated a 100 ppm sensitivity detection limit and a wide linear detection range of 200-2000 ppm at 100°C. This outstanding optical ethanol sensing performance can be ascribed to the very large surface area to volume ratio of this material, which increases the density of active sites for ethanol adsorption and reaction with adsorbed oxygen species.