Antimony-based bismuth-doped thin film, a new kind of super-resolution mask layer, is prepared by magnetron sputtering. The structures and optical constants of the thin films before and after annealing are examined in detail. The as-deposited film is mainly in an amorphous state. After annealing at 170–370 oC, it is converted to the rhombohedral-type of structure. The extent of crystallization increased with the annealing temperature. When the thin film is annealed, its refractive index decreased in the most visible region, whereas the extinction coefficient and reflectivity are markedly increased. The results indicate that the optical parameters of the film strongly depend on its microstructure and the bonding of the atoms.