Interfaces of pseudomorphic (100) ZnSe/GaAs heterostructures grown by molecular beam epitaxy have been studied by transmission electron microscopy. The observation of three different heterostructures suggests the existence of a transition structure at the ZnSe/GaAs interfaces which have formed on As‐deficient GaAs surfaces. The transition structure appears as a bright line in dark field images of the 200 reflection, while it becomes a dark line in dark field images of the 400 reflection. These observations are explained by assuming the existence of an interface layer which has a zinc blende type structure having vacancies in one of the face centered cubic sublattices.