New atomic-level experimental data on the intermolecular non-covalent interactions between a common odorant and a relevant residue at odorant binding sites are reported. The preferred arrangements and binding interactions of fenchone, a common odorant and ethanol, a mimic of serine's side chain, have been unambiguously identified using a combination of high resolution rotational spectroscopy and computational methods. The observed conformers include homochiral (RR) and heterochiral (RS) conformers, with a slight preference for a heterochiral form, and exhibit primary O⋯H–O hydrogen bonds between fenchone and ethanol. Secondary interactions play a key role in determining the relative configurations of fenchone and ethanol, and in shaping quite a flat potential energy surface, with many conformers close in energy and small barriers for interconversion.