Nanostructured metal oxide-based resistive-type gas sensors are of high research interest. Chemical stability is the most critical issue due to the surface electron species and density. In the present paper, 2D-nanostructured WO 3 was prepared and characterized, and a WO 3 -based sensor was fabricated and analyzed. The results showed that the synthesized WO 3 material exhibited nanosheet structure, and during hydrogen sensing testing, the current baseline shifted with various tendencies, even completely opposite directions under di®erent operation temperatures. The chemistry analysis results indicated that water molecule and hydroxyl group were formed under low operation temperature but further oxidation occurred at higher temperatures. The adsorption of H 2 on oxygen terminated WO 3 (0 0 1) surfaces by density functional theory (DFT) method indicated that a water molecule formed by adsorption of a hydrogen molecule at the O site with the most thermodynamically stable state, and two surface hydroxyl groups formed by dissociative adsorption with a thermodynamically less stable state. The water molecule and surface hydroxyl groups increased the conductivity of the WO 3¯l m while that was decreased as the oxidation occurred.