Silicon nanowires (SiNW) were formed on large grained, electron-beam crystallized silicon (Si) thin films of only ∼6 μm thickness on glass using nanosphere lithography (NSL) in combination with reactive ion etching (RIE). Electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM) studies revealed outstanding structural properties of this nanomaterial. It could be shown that SiNWs with entirely predetermined shapes including lengths, diameters and spacings and straight side walls form independently of their crystalline orientation and arrange in ordered arrays on glass. Furthermore, for the first time grain boundaries could be observed in individual, straightly etched SiNWs. After heat treatment an electronic grade surface quality of the SiNWs could be shown by X-ray photoelectron spectroscopy (XPS). Integrating sphere measurements show that SiNW patterning of the multicrystalline Si (mc-Si) starting thin film on glass substantially increases absorption and reduces reflection, as being desired for an application in thin film photovoltaics (PV). The multicrystalline SiNWs directly mark a starting point for research not only in PV but also in other areas like nanoelectronics, surface functionalization, and nanomechanics. © 2012 American Chemical Society.