Selective oxidation of the silicon element of silicon germanium (SiGe) alloys during thermal oxidation is a very important and technologically relevant mechanism used to fabricate a variety of microelectronic devices. We develop here a simple integrative approach involving vapor−liquid−solid (VLS) growth followed by selective oxidation steps to the construction of core−shell nanowires and higher-level ordered systems with scalable configurations. We examine the selective oxidation/ 16 condensation process under nonequilibrium conditions that gives rise to spontaneous formation of core−shell structures by germanium condensation. We contrast this strategy that uses reaction-diffusion-segregation mechanisms to produce coherently strained structures with highly configurable geometry and abrupt interfaces with growth-based processes which lead to low strained systems with nonuniform composition, three-dimensional morphology, and broad core−shell interface. We specially focus on SiGe core−shell nanowires and demonstrate that they can have up to 70% Ge-rich shell and 2% homogeneous strain with core diameter as small as 14 nm. Key elements of the building process associated with this approach are identified with regard to existing theoretical models. Moreover, starting from results of ab initio calculations, we discuss the electronic structure 23 of these novel nanostructures as well as their wide potential for advanced device applications.