X‐ray photoelectron spectroscopy studies of CdTe‐GaAs interfaces are reported. The growth start of CdTe on GaAs can be nearly stoichiometric if convenient growth parameters are chosen. The valence‐band offset between these two materials is found to be large (470 meV). Cd‐Te‐metal‐GaAs multilayers have been grown with very thin metal films. The CdTe‐GaAs band offset is not influenced by such intermediary metal layers. The experimentally obtained value for the valence‐band offset is compared with recent theoretical calculations taking into account interface dipoles.