The paper investigated nano-crystallization on surface layer of commercial pure titanium by using high-energy shot peening. The grain size and the microstructure in deformed surface layer by high-energy shot peening are analyzed with X-ray diffraction and TEM etc. In addition, the variations of surface microhardness are examined after high-energy shot peening. The results described that the nano-crystalline surface layer have been formed in commercial pure titanium with a structure of hexagonal closet packet, by high-energy shot peening. The surface microhardness increases and the grain size in nano-crystalline surface layer diminishes, with increasing the time in high-energy shot peening. The minimum nano-crystalline grain size is approximately 40 nm.