Se0.8S0.2 chalcogenide glass films have been prepared by thermal vacuum evaporation technique with thickness 583 nm. Annealing process at T >= 333 K crystallizes the films and nanostructured films are formed. The crystallite size was increased to 24 nm as the annealing temperature increased to 373 K. Orthorhombic crystalline system was identified for the annealed films. SEM micrographs show that films consist of two parallel surfaces and the thickness was determined by cross section imaging. The optical transmittance is characterized by interference patterns as a result of these two parallel surfaces, besides their average value at longer wavelength decreases as a result of annealing process. The band gap, E-g is red shifted due to crystallization by annealing. As the phase of the films changes from amorphous to crystalline in the annealing temperature range 333-363 K, a non sharp change of the band gap (E-g) is observed. This change was explained by Brus's model of the energy gap confinement behavior of the nanostructured films. The optical refractive index increases suddenly when the system starts to be crystallized by annealing. (C) 2008 Elsevier B.V. All rights reserved.