The interface formation between vacuum evaporated CdS and ultrahigh vacuum-cleaved CuInS2 single crystals has been studied by synchrotron excited photoelectron spectroscopy. The valence band discontinuity is determined directly from valence band difference spectra to be Delta E(V)=0.6 (+/-0.1) eV. This value is significantly smaller than for other preparation conditions given in the literature and evidently not suitable for solar cell applications. The similarity to observations at the the CdS/CuInSe2 interfaces suggests that neutrality levels play a dominant role in establishing the band lineup at interfaces containing chalcopyrite semiconductors. (C) 1997 American Institute of Physics.