A previously undetected conformer of propan-1,2-diol has been detected and analyzed by Fourier transform microwave spectroscopy. A simultaneous ab initio investigation predicted this conformation to be the global minimum on the potential energy surface and comparison of the transition intensities supported this view. Detection of the 13C and 2H isotopomers enabled a Kraitchman-type determination of the structure to be performed. The results matched well with the theoretical predictions. © 2002 Elsevier Science B.V. All rights reserved.