A novel approach to pattern nanocrystalline gold (Au) octahedra is presented based on electron irradiation combined with thermal treatment and post-cleaning process using HAuCl4-loaded poly(styrene-b-2-vinyl pyridine) (PS-b-P2VP) block copolymer (BCP) as a precursor material. The BCP tends to cross-link under electron irradiation, and thus a patterned film can be prepared by selectively irradiating an electron beam onto a precursor film using a shadow mask. A post-thermal treatment leads to the formation of crystalline Au nano-octahedra inside the patterned film with a help of the BCP acting as a capping agent. Subsequently, the BCP can be removed by O-2 plasma etching combined with oxidative degradation, with the Au nanoparticles remaining. As a result, a patterned film consisting of high-purity nanocrystalline Au octahedra is fabricated. The sizes of the Au octahedral nanoparticles can be readily controlled from 49 to 101 nm by changing the thickness of the precursor film. The patterned Au nano-octahedra films exhibit excellent surface-enhanced Raman scattering behavior with the maximum enhancement factor of similar to 10(6).