The effects of composition and thermal annealing near crystallization temperature, T_c on the optical and structural properties of Ge₂₀Se_80−xBi_x (x=0, 2.5, 5 and 7.5 at%) was investigated. The influence of incorporation Bi content in Ge₂₀Se_80−xBi_x system results in a gradual decrease in the indirect optical gap from 1.89 to 1.44 eV, this behavior can be explained as increased tailing. On annealing, the optical band gap E_g decreases gradually for the crystallized films while the refractive index increases, this behavior can be attributed to transformation from amorphous to crystalline and was explained in the light of dangling bond model. The refractive index n of as-prepared and annealed films has been analyzed according to the Wwmple–DiDominico single oscillator model and the values of E_o and E_d were determined. The effect of annealing on the nature and degree of crystallization has been investigated by …