In structural hierarchy, inherently hollow nanostructured materials preferentially possessing high surface area demand attention due to their alluring sensing performances. However, the activity of hollow and structural hierarchy nanomaterials generally remains suboptimal due to their hollow space structure and large lateral size, which greatly hamper and limit the availability of inner space active sites. Here, hollow ZnSnO3 cubes with a controllable interior structure were successfully prepared through a simple and low-cost coprecipitation approach followed with a calcination process. The solid-, single-, double-, and multishelled ZnSnO3 hollow cubes could be selectively tailored by repeated addition of alkaline solution. The multishelled architecture displayed outstanding sensing properties for formaldehyde vapors due to large specific surface area, less agglomerations, abundant interfaces, thin shells, and high proportion porous structure, which act synergistically to facilitate charge transfer and promote target gas adsorption.