Silicon surfaces with nanoscale etched patterns were obtained using polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer films as templates, followed by brief immersion in HF(aq). The resulting interfaces were comprised of pseudohexagonal arrays of pits on the silicon, whose shapes depended upon the chosen silicon orientation. The top unetched face of silicon remains capped by the native oxide, and the pit interiors are terminated by Si-H x. Selective chemical functionalization via these two chemical handles was demonstrated to be a viable approach toward building nanostructured metal oxide and metal features within these silicon pits and on the top face. Using a series of interfacial chemical reactions, including oxidation (of Si-H x-terminated regions), hydrosilylation, and alkoxysilane-based chemistry on silicon oxide, the growth of metal-based structures can be spatially controlled. In the first approach, titania nanobowls were grown within the etch pits, and in the second, galvanic displacement was used to produce gold nanoparticles either within the etch pits, on the top silicon face, or both. © 2011 American Chemical Society. ; peer reviewed: yes ; NRC Pub: yes