We present evidence that the critical thickness for the appearance of misfit defects in a given material and heteroepitaxial structure is not simply a function of lattice mismatch. We report substantial differences in the relaxation of mismatch stress in Ge0.5Si0.5/Si superlattices grown at different temperatures on (100) Si substrates. Samples have been analyzed by x‐ray diffraction, channeled Rutherford backscattering, and transmission electron microscopy. While a superlattice grown at 365 °C demonstrates a high degree of elastic strain, with a dislocation density<105cm−2, structures grown at higher temperatures show increasing numbers of structural defects, with densities reaching 2×1010cm−2at a growth temperature of 530 °C. Our results suggest that it is possible to freeze a lattice‐mismatched structure in a highly strained metastable state. Thus it is not surprising that experimentally observed critical thicknesses are rarely in agreement with those predicted by equilibrium theories.