The hollow and porous structured materials usually show improved physical and chemical properties. Here, we report the successful synthesis of hierarchical ZnSnO3 nanocubes via a simple yet facile hydrothermal method. The as-prepared hierarchical ZnSnO3 nanocubes exhibit hollow, porous architectures, and have a larger specific surface area than solid ZnSnO3 nanocubes. Through a comprehensive characterization of nanostructures and morphology evolution of the as-prepared products, we find that F ions play a critical role in producing such unique hollow, porous architectures. We further proposed a possible growth mechanism for the hollow, porous ZnSnO3 nanocubes. Consequently, the sensor made of hollow and porous ZnSnO3 nanocubes is found to show good gas sensing performance to ethanol gas even at the low concentrations by doping of F. (C) 2016 The Electrochemical Society. All rights reserved.