The polyhedral crystals, octahedral crystals and cube crystals of Zinc hydroxystannate (ZHS) were prepared by the homogeneous precipitation synthesis method. The organic compounds, PEG-400, β-cyclodextrin (β-CD) and L-alanine were added in the reaction systems to control the crystal structure. The crystal structure and morphology of products were characterized by SEM and XRD. The crystal structure of all products could be attributed to the cubic ZnSn(OH)6 by the XRD analysis. The SEM pictures of the products were different with the change of organic compounds. The FTIR spectrum indicated the ZHS without organic residual and the possible formation mechanism was discussed.