Tin oxide (SnO₂) is considered a very promising material as a high capacity Li-ion battery anode. Typically, the electrochemical performance of tin oxide based anodes is dependent on various factors such as their size and composition. Here, we demonstrate how defined dispersion of nanostructures can improve the understanding of the relationship between the electrode performance and its architecture. Two different types of well-defined hierarchical Sn@SnO₂ core-shell nanoparticle dispersions were prepared by molecular beam epitaxy (MBE) on silicon, composed of either amorphous or polycrystalline SnO2 shells. Sn doped In₂O₃ (ITO) NP dispersions are also demonstrated from MBE nanoparticle growth. Preparation of SnO₂ and related materials by highly defined MBE growth as a model system allows a detailed examination of the influence of material dispersion or nanoarchitecture on the performance of active electrode materials.