We observed the rotational spectrum of the 1:1 molecular adduct between 2-phenylethylamine and water (normal and H(2)(18)O species) by free jet absorption microwave spectroscopy in the frequency region 60-78 GHz. The dominant spectrum belongs to the structure where the PEA moiety is in the most stable gauche conformation and the water molecule is hydrogen bound to the nitrogen lone pair. The orientation of the water molecule is such that the oxygen atom is almost equidistant (ca. 2.5 A) from the closest methylenic and aromatic hydrogen atoms.