Ga-catalyzed growth of GaAs nanowires on Si is a candidate process for achieving seamless III/V integration on IV. In this framework, the nature of silicon's surface oxide is known to have a strong influence on nanowire growth and orientation and therefore important for GaAs nanowire technologies. We show that the chemistry and morphology of the silicon oxide film controls liquid Ga nucleation position and shape; these determine GaAs nanowire growth morphology. We calculate the energies of formation of Ga droplets as a function of their volume and the oxide composition in several nucleation configurations. The lowest energy Ga droplet shapes are then correlated to the orientation of nanowires with respect to the substrate. This work provides the understanding and the tools to control nanowire morphology in self-assembly and pattern growth.