ZnS nanotetrapods were investigated by atom-resolved microscopy characterization and quantitative simulation. The octahedron core enclosed with Zn- and S-terminated surfaces was verified. Four hexaprism-shaped arms were selectively grown from Zn-terminated surfaces of the core by alternately stacking zinc blende and wurtzite structures. The stacking order change at the core/arm interface is significant to activate the arm growth. The anisotropic growth mechanism was proposed and further proved by the synthesis of ZnS nanoparticles and nanobelts. © 2011 American Chemical Society.