Peptide-based self-assembled monolayers (SAMs) are well known to be crucial for biocompatible surface formation on inorganic substrates applied for implants, biosensors, or tissue engineering. Moreover, recently these bioinspired nanostructures are also considered particularly interesting for molecular electronics applications due to their surprisingly high conductance and thickness-independent capacitance, which make them a very promising element of organic field-effect transistors (OFETs). Our structural analysis conducted for a series of prototypic homooligopeptides based on glycine (Gly) with cysteine (Cys) as a substrate bonding group chemisorbed on Au and Ag metal substrates (GlynCys/Au(Ag), n = 1-9) exhibits the formation by these monolayers secondary structure close to β-sheet conformation with pronounced odd-even structural effect strongly affecting packing density and conformation of molecules in the monolayer, which depend on the length of molecules and the type of metal substrate. Our experiments indicate that the origin of these structural effects is related to the either cooperative or competitive relationship between the type of secondary structure formed by these molecules and the directional character of their chemical bonding to the metal substrate. The current analysis opens up the opportunity for the rational design of these biologically inspired nanostructures, which is crucial both for mentioned biological and electronic applications.