Enhanced synthetic control of the morphology, crystal structure, and composition of nanostructures can drive advances in nanoscale devices. Axial and radial semiconductor nanowires are examples of nanostructures with one and two structural degrees of freedom, respectively, and their synthetically tuned and modulated properties have led to advances in nanotransistor, nanophotonic, and thermoelectric devices. Similarly, developing methods that allow for synthetic control of greater than two degrees of freedom could enable new opportunities for functional nanostructures. Here we demonstrate the first regioselective nanowire shell synthesis in studies of Ge and Si growth on faceted Si nanowire surfaces. The selectively deposited Ge is crystalline and its facet position can be synthetically controlled in situ. We use this synthesis to prepare electrically-addressable nanocavities into which solution soluble species such as Au nanoparticles can be incorporated. The method furnishes multi-component nanostructures with unique photonic properties and presents a more sophisticated nanodevice platform for future applications in catalysis and photodetection.Semiconductor nanowires (NWs) represent a diverse class of nanomaterials whose synthetically-tunable structural, electronic, and optical properties 1-3 have enabled active nanodevices including high-performance field-effect transistors, 4 ultra-sensitive biological probes, 5-7 and solar cells and photonic devices with tunable optical spectra. [8][9][10][11][12] NWs can be classified according to the number of degrees of freedom (DoF) they possess, which represent fundamental physical coordinates along which their structure can be manipulated. Axial and radial (core/shell) modulated NWs have 1 and 2 DoF, respectively, and have been extensively studied and characterized. 2,[13][14][15][16][17][18][19] Nevertheless, the properties of nanostructures possessing greater complexity and anisotropy have not been determined.A nanostructure with 3 DoF and higher can be realized by breaking the rotational symmetry of conventional radial shell growth ( Figure 1A). A high-resolution scanning electron micrograph (SEM) of a faceted core/shell Si NW ( Figure 1B) reveals well-defined surfaces that were previously indexed 9 as {111}, {011}, and {113}. NWs with this same morphology and set of surface facets serve as the faceted templates from which all subsequent nanostructures in this study are grown. Following chemical vapor deposition (CVD) synthesis of the SiNW templates, 9 introduction of GeH 4 and H 2 at lower tem- perature and pressure into the same reactor (Supporting Information) yields a new product featuring selective material deposition on the {111} and {011} Si surface facets ( Figure 1B). Energy dispersive x-ray spectroscopy (EDS) performed on the nanostructure ( Figure 1C) confirms the elemental identity of the deposited material as Ge and reveals that facet selectivity is preserved along the length of the nanostructure. A planview transmission electron micrograph (...