We studied the growth and electronic structure of the ZnTe/CdTe(100) interface with angle‐resolved synchrotron radiation photoemission (ARPES) and reflection high energy electron diffraction (RHEED). RHEED patterns during the growth of ZnTe layers on the CdTe(100) substrate showed that the initial ∼16 A˚ grows in registry. After this pseudomorphic 16 A˚ layer, the next 120 A˚ grows with defects to relieve the 6.6% strain between ZnTe and CdTe. After ∼140 A˚, the ZnTe layers are relaxed. ARPES taken near the Brillouin zone center gave a valance band offset &Dgr;Ev=0.14 eV, with the ZnTe valence band maximum (VBM) higher than the CdTe VBM.