The metastable state hexagonal-tungsten oxide (h-WO3) has been attracting attention over the past decade because of its high reactivity that arises from the hexagonal channels in its crystal structure. Simplification of the process used to synthesize h-WO3 is an important step to facilitate the industrial applications of this material. In this study, we addressed this challenge by developing a spray pyrolysis process to synthesize highly crystalline h-WO3. The ratio of the monoclinic to the hexagonal phase was controlled by adjusting the segregation time. Single-phase h-WO3 nanorods were synthesized using a carrier gas flow rate of 1 L/min, which was equivalent to a segregation time of 18.4 s. The ability of the h-WO3 nanorods to adsorb nitrogen and carbon dioxide was evaluated to confirm the presence of hexagonal channels in the crystal structure. (C) 2018 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.