Nanostructured mesoporous materials are widely used for many practical applications due to their large, controllable pore size, and high surface area. With its large specific surface area for more reactive sites and narrow pore size distribution, mesoporous tungsten oxide used as a semiconducting ceramic material is now attracting attention in various applications, such as gas sensing, electrochromic apparatus, and optical devices. This chapter provides a new method to prepare wormhole‐like mesoporous tungsten oxide by a reflux process, which is indicative of the filling of wormhole‐like mesopores dispersed and thermally stabilized in tungsten oxide. It proposes a possible model to govern or suppress the grain growth of wormhole‐like mesoporous tungsten oxide. Wormhole‐like mesoporous tungsten oxide can thus retard the collapse rate of mesopores during the calcination process. These results are of great significance for the control of porous micro‐structure, crystallinity, and applications for the development of nanostructured mesoporous tungsten oxide.