The band alignment at polycrystalline CdS/CdTe heterointerfaces for thin-film solar cells is determined by photoelectron spectroscopy from stepwise CdTe deposition on polycrystalline CdS substrates and from subsequent sputter depth profiling. Identical values of 0.94+/-0.05 eV for the valence band offset are obtained. (C) 2002 American Institute of Physics.