Zinc stannates (Zn2SnO4) with different morphologies and crystal structures were synthesized via low-temperature hydrothermal method in the presence of various alkaline mineralizers. Zn2SnO4 generally crystallizes into an inverse spinel crystal structure (cubic phase). However, we found that Zn2SnO4 could assembly into a slightly distorted cubic structure (quasi-cubic phase) for the first time by using tetrabutylammonium hydroxide as an alkaline mineralizer. In addition, we successfully tuned the morphologies of the as-prepared Zn2SnO4 particles, from cube, cuboctahedron, truncated octahedron, to octahedron, by adjusting the type and the concentration of alkaline mineralizers and surfactants. Compared with cubic Zn2SnO4, the quasi-cubic Zn2SnO4 showed a noticeable red shift of the band gap, and the gas sensors based on quasi-cubic Zn2SnO4 exhibited high sensitive performance to alcohol. XPS analyses revealed that the shift of Zn 2p(3/2) binding energy in the quasi-cubic Zn2SnO4, which indicated some Zn ions in quasi-cubic Zn2SnO4 adopted different coordination environments from regular tetrahedral/octahedral ones adopted in cubic Zn2SnO4. (C) 2011 Elsevier B.V. All rights reserved.