Cu-rich Cu(In, Ga)Se2 (CIGS) films were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive x-ray fluorescence spectroscopy (EDX) and x-ray photoelectron spectroscopy (XPS). The Cu-rich CIGS film were treated in KCN and NH3 solutions. In the as-deposited Cu-rich CIGS film, the cation ratio of Cu/(In+Ga) at the surface exceeded the bulk value. Cross-sectional TEM of the KCN-treated film suggested that Cu2-xSe existed both at the grain boundaries and on the grains near the surface of the Cu-rich CIGS film. The Cu2-xSe was completely removed by the treatment in the KCN solution and was removed only at the front surface by treatment in the NH3 solution.