This work focuses on the synthesis and interfacial characterization of gold nanostructureson silicon surfaces, including Si(111), Si(100), and Si nanowires. The synthetic approach uses galvanic displacement, a type of electroless deposition that takes place in an efficient manner under aqueous, room-temperature conditions. The case of gold-on-silicon has been widely studied and used for several applications and yet, a number of important, fundamental questions ras to the nature of the interface. Some studies are suggestive of heteroepitaxial growth of gold on the silicon surface, whereas others point to the existence of a silicon-gold intermetallic sandwiched between the metallic gold and the underlying silicon substrate. Through detailed high resolution transmission electron microscopy (TEM), combined with selected area electron diffraction (SAED) and nanobeam diffraction (NBD), heteroepitaxial gold that is grown by galvanic displacement is confirmed on both Si(100) and Si(111), as well as silicon nanowires. The coincident site lattice (CSL) of gold-on-silicon results in a very small 0.2% lattice mismatch due to the coincidence of four gold lattices to three of silicon. The presence of gold-silicon intermetallics is suggested by the appearance of additional spots in the electron diffraction data. The gold-silicon interfaces appear heterogeneous with distinct areas of heteroepitaxial gold on silicon, and others, less well-defined, where intermetallics may reside. The high resolution cross-sectional TEM images reveal a roughened silicon interface under these aqueous galvanic displacement conditions, which most likely promotes nucleation of metallic gold islands that merge over time: a Volmer-Weber growth mechanism in the initial stages. © 2009 American Chemical Society ; peer reviewed: yes ; NRC Pub: yes