Direct characterization of band alignment at chemical bath deposition (CBD)-CdS/Cu0.93 (In1-xGax)Se2 has been carried out by photoemission spectroscopy (PES) and inverse photoemission spectroscopy (IPES). Ar ion beam etching at the condition of the low ion kinetic energy of 350 eV yields a removal of surface contamination as well as successful measurement of the intrinsic properties of each layer and the interfaces. Especially interior regions of the wide gap CIGS layers with a band gap of 1.4 ∼ 1.6 eV were successfully exposed. IPES spectra revealed that the conduction band offset (CBO) at the interface region of the wide gap CIGS with x = 0.60 and 0.75 was negative, where the conduction band minimum of CdS was lower than that of CIGS. It was also observed that the energy spacing between conduction band minimum (CBM) of CdS layer and valence band maximum (VBM) of Cu0.93(In0.25Ga0.75)Se2 layer at interface region was no wider than that of the interface over the Cu0.93(In0.60Ga0.40)Se2 layer.