We studied the DFT (B3LYP) and HF at 6-31+G/6-31+G∗∗ levels of theory in order to throw light on the conformation, structure, intramolecular hydrogen bond network, as well as proton and nitrogen NMR (GIAO method) of a series of model primary amides in the gas phase and/or in solution (chloroform, methanol, water, dimethyl sulfoxide, and heptane). In this manner, it was possible to show that the amidic group of these model compounds acts as the H-bond donor and interacts with two different H-bond acceptors, thus stabilizing the C8 pseudocycle. The study was conducted to gain a better understanding of the conformation (both experimentally and theoretically) adopted by hydrazino acetamides (model compounds for aza-β3-peptides). In the light of this, we were able to explain why aza-β3-peptides develop a different H-bond network in comparison to their isosteric β3-peptide analogues (an extension of the β-peptide concept).