We report the growth of high quality ZnSe/GaAs superlattices by migration‐enhanced epitaxy (MEE) and their characterization using x‐ray diffraction, electron microscopy, and photoluminescence. A streaky reflection high‐energy electron diffraction (RHEED) pattern and strong, persistent RHEED oscillation during the MEE growth of the superlattices indicate a smooth growing surface. The sharp satellite peaks observed clearly in the double‐crystal x‐ray diffraction rocking curve of a 21‐period ZnSe/GaAssuperlattice confirm the excellent crystalline and interfacial quality of the superlattice. Cross‐section high‐resolution electron microscopy indicates coherent lattice arrangement and abrupt interface at ZnSe‐on‐GaAs as well as GaAs‐on‐ZnSe heterointerfaces. Photoluminescence spectra from a superlattice with a periodicity of 40 nm show a strong peak at a wavelength of 829.5 nm with a linewidth of 6.3 meV at a temperature of 10 K; we believe this to be the first observation of photoluminescence from any multilayer structure involving GaAs‐on‐ZnSe growth.