The vaporization enthalpies of 1,2- ethanediol through 1,10- decanediol, 1,12- dodecanediol, 1,14- tetradecanediol, 1,16- hexadecanediol, 1,4- butynediol, 2,5- dimethyl- 3- hexyne- 2,5- diol, and 2,5- dimethyl- 3- hexane- 2,5- diol are examined by correlation gas chromatography. A good correlation is observed between the mean literature values and the enthalpies of transfer from solution to the gas phase for all the alpha,omega- alkanediols examined. Intramolecular hydrogen bonding in the liquid phase of the smaller 1,omega- alkanediols does not appear to be very important thermochemically and appears to have a minimal effect in the gas phase as judged by the vaporization enthalpies of 1,4- butynediol, 1,4- butanediol, 2,5- dimethyl- 3- hexyne- 2,5- diol, and 2,5- dimethylhexane- 2,5- diol. The sublimation enthalpies of the alpha,omega- alkanediols were calculated as the sum of the fusion and vaporization enthalpies at T) 298.15 K.