Semiconductor nanowires refer to crystal structures with diameters as small as a few nanometers and lengths up to tens of micrometers or even millimeters. Nanowires can be produced either through conventional subtractive nanofabrication processes, via lithography and etching, or through additive nanomaterial growth methods. The quality of “top-down” fabricated nanowires are in principle determined by the starting material, although the size reduction techniques used to fabricate these structures inevitably introduce damage (e.g., roughness) that can degrade overall quality. The top-down approach, which relies heavily on the precision of the lithography and etching tools, also becomes less cost-effective when scaling to ca. 10 nm size regimes. In this chapter we focus on nanowires produced through “bottom-up” growth methods, in which the critical dimension (e.g. the nanowire diameter) is limited not by lithography precision but controlled during chemical synthesis with atomic resolution. In particular, the catalyst-mediated vapor–liquid–solid (VLS) process is discussed in detail since this approach enables the growth of a broad range of nanowire materials with controlled structure, morphology, composition, and doping.