Infrared-ultraviolet double-resonance spectroscopy has been applied to discriminate rotamers of jet-cooled aryl alcohol homologues, φ-(CH₂)_nOH, where φ represents phenyl group and n=1, 2, and 3 correspond to benzyl, phenethyl, and 3-phenylpropyl alcohols, respectively. Experimental results indicate that different OH stretching frequencies are associated with different rotamers and that the ability of intramolecular hydrogen bonding with the benzene π-electron decreases with an increase in alkyl chain length. in each aryl alcohol, the most prominent species in jets corresponds to the non-hydrogen bonded rotamer having higher OH stretching frequency.