We have detected one conformer of 2-phenylethanol and determined its shape using Stark-modulated free jet microwave spectroscopy. By comparing observed and ab initio predicted spectroscopic rotational constants and hydroxyl-deuteration isotopic substitution coordinates, the species has been identified with a gauche conformer, designated as 1, in which the hydroxyl hydrogen atom is involved in an intramolecular hydrogen bond with the pi-electron cloud of the aromatic ring. Stark effect measurements yielded electric dipole moment values of mu(a) = 1.251(3) D and (mu(b)(2) + mu(c)(2))(1/2) = 1.102(10) D, and hence mu(total) = 1.667(10) D. Previously published molecular mechanics and RHF level ab initio calculations predict that other conformers are of comparable stability to 1. However, when electron correlation is included at the MP2/6-31G(d,p) level, the predicted energy of 1 is substantially (ca 8 kT mol(-1)) lower than that of all the other conformers. This is in full accord with our identification of only one conformer in our spectroscopic Searches at a pre-expansion temperature of 363 K.