The technology of heteroepitaxially growing compound semiconductors, particularly GaAs, on Si has attracted an increasing volume of attention in the past 3–5 years. In the past two years there have been few major advances in the growth recipes, which all include a high temperature Si preheat, a two-step growth temperature profile, and the use of misoriented substrates. The need for mechanistic understanding of the effect of these parameters is crucial to advancing the state of the art beyond this current practice. This work focusses on the effect of the misorientation in inducing asymmetry in early stages of the molecular beam epitaxy of GaAs on Si substrates. The strain in the films is found to have greatly different rates of relaxation in the plane of the film when measured in the two orthogonal <220> directions. This asymmetry persists to greater than 30 nm film thickness at 400°C. The nucleation morphology was also examined as a function of substrate misorientation. At low substrate tilts, nucleation density was sparse and there was not substantial ordering of the nuclei. As the tilt was increased, a distinct habit emerged where collections of nuclei were quite coherent along the steps for several 100 nm, with dimensions of the order of 10's of nm perpendicular to the steps. The density of steps with nuclei was also substantially less than that predicted by the widely accepted “array of double-height steps” used to explain the curious lack of anti-phase disorder in these films.