Star-like ZnO nanostructures were grown on SI(100) substrates with carbon(C) catalyst by employing vapor-solid(VS) mechanism. The morphologies and structure of ZnO nanostructures were investigated by Field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and Raman spectrum, Photoluminescence spectrum. The results demonstrated that the as-synthesized products consisted of star-like ZnO nanostructure with hexagonal wurtzite phase. Nanostructures grown at 1100 were mainly star-like in structure with diameters of 500 nm. The legs of the star-like nanostructures were preferentially grown up along the [0001] direction. A vapor.solid (VS) growth mechanism was proposed to explain the formation of the star-like structures. Photoluminescence spectrum exhibited a narrow emission band peak around 380 nm and a broad one around 491 nm. Raman spectrum of the ZnO nanostructures showed oxygen defects in ZnO nanostructures due to the existence of Ar gas during the growth process, leading to the dominant green band peak in the PL spectrum.