We report the results of our studies on the optical and electronic structure of a wide range of polycrystalline thin-film CuIn1-xGaxSe2 (CIGS) alloys. The composition range includes CIS and nearly stoichiometric (slightly Cu-poor) (24.3±0.3 at.% Cu) CIGS with x values located around the value that has the best efficiency (x ∼ 0.28). Relative to nearly stoichiometric CIS and CIGS, we find a reduction in the absorption strength in the spectral range 1-3 eV. This reduction can be explained in terms of the predominance of Cu 3d and Se 4p states at the valence band maximum (VBM). In addition, Cu-poor CIS and CIGS materials show an increase in bandgap because the p-d repulsive interaction in Cu-poor CIGS is less than that in nearly stoichiometric CIGS. High efficiency is discussed in terms of optical properties.