Single-crystalline zinc hydroxystannate (ZnSn(OH)(6)) microcubes are synthesized on ITO glass substrates using a hydrothermal growth method. Scanning electron microscopy shows the as-grown zinc hydroxystannate microcubes are structurally perfect and regular, with edge length of similar to 5-8 mu m. X-ray diffraction, the selected area electron diffraction and the high-resolution transmission electron microscopy indicate that the as-grown zinc hydroxystannate microcubes are single crystalline with the cubic perovskite crystalline structure, and [2 0 0] is the preferential growth direction. Both the concentration of the Sn(OH)(6)(2-) ions and the molar ratio of NaOH to SnCl4 are found to play important roles in determining the size and the shape of the zinc hydroxystannate crystalline. The possible growth mechanism of the zinc hydroxystannate crystalline is believed to be a dissolution-precipitation process. (C) 2007 Elsevier B.V. All rights reserved.