We report a detailed study of the effect of lattice mismatch on ZnSe epilayers grown on ⟨001⟩ GaAs by molecular beam epitaxy using photoluminescence (PL), x‐ray diffraction, and transmission electron microscopy (TEM) techniques. We find that our samples are of high quality, exhibiting sharp and strong bound excitons, and that these bound excitons shift to higher energies due to tetragonal distortion as the thickness of the ZnSe epilayer is systematically reduced from ∼1 to 0.1 &mgr;m. Fairly good agreement is found between PL and x‐ray data for the total strain relaxation as a function of layer thickness. TEM measurements are also used to estimate an inelastic component of the strain relaxation in the layers.