Here, we describe the unusual self-assembly of amine-terminated oligoglycine peptides into extended two-dimensional sheets in the presence of silver nanowires. The resulting tectomer sheets are shown to have a strong affinity for the nanowires through a charge-transfer interaction as evidenced by X-ray photoelectron spectroscopy. We show that extended assemblies of metal–peptide hybrids offer additional augmentative functionalities; for instance, the tectomer sheets are hydrophobic in nature and act as a protective layer preventing oxidation and degradation of the nanowires when exposed to atmospheric conditions. Moreover, for silver nanowire percolating networks the presence of the peptide markedly increases the overall electrical conductivity through mechanical squeezing of wire–wire junctions in the network. The peptide–metal interface can be controlled by pH stimulus thus potentially offering new directions where silver nanowire assemblies are used for transparent electrodes ranging from antimicrobial coatings to biosensors.