A novel hierarchical polygon prismatic nanostructure of wurtzite Zn has been grown on silicon by liquid-solution seed nucleation and vapor-gas growth method. The Zn(ClO4)2 colloidal sol with various concentrations was used as seeds to control the dimension of Zn crystals from the nanometer (30 nm) to micrometer scale (2 μm). Depending on heat-treatment temperature, different morphology was developed. In the temperature range of 200-300°C, a compact polygon prismatic Zn structure was formed. However, in a high temperature range of 300-400°C, polygon prismatic Zn with hollow structure was observed. After oxidation treatment, the ZnO surface layer can be developed on the Zn nanocrystals to form ZnO-Zn core-shell structure as evidenced from PL measurement. These formed ZnO-Zn nano- and micro-crystals can be further used as building blocks to assemble two- or three-dimensional photonic crystals.