We studied the structural and electronic properties of the ZnTe/CdTe(100) interface with reflection high‐energy electron diffraction and angle‐resolved synchrotron radiation photoemission spectroscopy (ARPES). ZnTe overlayers grown at 300 °C on CdTe(100) were fully strained and pseudomorphic up to ≊16 A˚. Beyond this coverage the ZnTe film starts to gradually relax the 6.6% in‐plane lattice strain. Complete relaxation is reached at a ZnTe coverage of ∼300 A˚. A valence‐band offset of &Dgr;Ev=0.00±0.05 eV was measured with ARPES at the &Ggr; point. This propitious band lineup may allow for the use of a ZnTe intermediate layer at metal/CdTe structures to induce ohmic back contacts in CdS/CdTe heterojunction solar cells.