AgGaSe 2 thin films were deposited by flash evaporation onto Corning 7059 glass substrates maintained at 303 to 673 K. The EDAX and ESCA analysis revealed that the films formed at T s = 523–573 K were stoichiometric with at% of Ag, Ga and Se being 24.5, 24.9 and 50.6 respectively. XRD and TEM studies indicated that these films were polycrystalline with mean grain size of 550 nm, single phase and exhibited tetragonal chalcopyrite structure with a = 0.598 nm, c = 1.090 nm and ( c/ a) = 1.823. The absorption humps observed in the spectral range 1.5 to 3.0 eV, were attributed to valence sub-band transitions. (αhv) 2 vs energy curves indicated a direct fundamental gap of 1.75 eV. Band splitting by crystal-field and spin-orbit effects were observed at 1.95 and 2.20 eV, respectively. The crystal-field and spin-orbit parameters, the tetragonal compression, the deformation potential and the d level hybridization percentage were estimated using the quasi-cubic and linear hybridization models.