Spectroscopic ellipsometry measurements of CuInSe2 (CIS) and CuIn0.8Ga0.2Se2 (CIGS) reveal that there are important differences in electronic properties between stoichiometric CIS (CIGS) and Cu-poor CIS (CIGS). We find a reduction in the absorption strength in the spectral region of 1–3 eV. This reduction can be explained in terms of the Cu 3d density of states. Cu-poor CIS (CIGS) materials show an increase in band gap due to the reduction in repulsion between Cu 3d and Se 4p states. The experimental results have important implications for the function of polycrystalline optoelectronic devices.