The (Ga0.3In0.7)2Se3 films deposited by the thermal evaporation technique are annealed in the inert atmosphere (argon) for 1 h at temperatures of 50, 100, and 150 ∘C. The spectral ellipsometry is applied for measuring the spectral dependences of the refractive and extinction coefficients of as-deposited and annealed (Ga0.3In0.7)2Se3 films. The optical transmission spectra, as well as the optical absorption spectra of (Ga0.3In0.7)2Se3 films, are studied depending on the annealing temperature. The optical absorption edge for annealed (Ga0.3In0.7)2Se3 films is shifted to the short-wavelength region and broadens, as the annealing temperature increases. Parameters of the Urbach absorption edge are determined for as-deposited and annealed (Ga0.3In0.7)2Se3 films. The spectral dependences of the refractive index are analyzed in the framework of the Wemple–DiDomenico model. The nonlinear increase of the energy pseudogap, Urbach energy, and refractive index with the annealing temperature are revealed.