By combining ultraviolet and x-ray photoelectron spectroscopy with inverse photoemission spectroscopy, we find that the conduction-band alignment at the CdS/CuInSe2 thin-film solar- cell heterojunction is flat (0.0+/-0.2 eV). Furthermore, we observe a valence-band offset of 0.8+/-0.2 eV. The electronic level alignment is dominated by (1) an unusually large surface band gap of the CuInSe2 thin film (1.4 eV), (2) by a reduced surface band gap of the CdS overlayer (2.2 eV) due to intermixing effects, and (3) by a general influence of the intermixing on the chemical state near the interface