CdS/CuInSe2 (CIS) heterojunctions were investigated by XPS analysis. An In-excess layer which may form an ordered vacancy compound (OVC) was present at the as-deposited CIS surface and it remained after chemical bath deposition of a CdS layer. The In-excess layer was removed by preferential etching with NH3 aqueous solution. This result implies that the surface of the as-deposited CIS film was converted from the OVC with n-type conductivity into the CIS with p-type by NH3 treatment. The conduction band offsets at the CdS/p-CIS and CdS/n-OVC were determined to be 1.0 and 0.3 eV, respectively. The CIS solar cells fabricated with n-OVC surface layer exhibited higher cell efficiencies than those fabricated with p-CLS surface layer.