Solid samples of phenylglycinol were vaporized by laser ablation and investigated through rotational spectroscopy in a supersonic expansion using two different techniques: chirped pulse Fourier transform microwave spectroscopy and narrow band molecular beam Fourier transform microwave spectroscopy. One conformer, bearing an O-H center dot center dot N and an N-H center dot center dot center dot pi intramolecular hydrogen bonds, could be successfully identified by comparison of the experimental rotational and N-14 nuclear quadruple coupling constants with those predicted theoretically. (C) 2014 Elsevier B.V. All rights reserved.