The desorption of methanol (MeOH), propan-1-ol (n-PrOH), propan-2-ol (i-PrOH) and 2-methylpropan-2-ol (t-BuOH) from Na+-, Ca2+-, Al3+-, Cr3+- and Fe3+-exchanged montmorillonite has been studied using variable temperature infrared (IR) spectroscopy and thermogravimetric analysis (TGA). Alcohol-saturated trivalent cation (M3+) exchanged samples exhibit maxima in the derivative thermograms at 20 and 110°C (MeOH), 30 and 160°C (n-PrOH), 20 and 110°C (i-PrOH) and 20, 55 and 80°C (t-BuOH). Alcohol-saturated Na+ and Ca2+-exchanged montmorillonite samples exhibit maxima at higher temperatures in the i-PrOH (20 and 140°C) and t-BuOH (30, 90 and 110°C) desorption profiles but at the same temperatures for MeOH and n-PrOH. Mass spectroscopic analysis of the vapours desorbed from the alcohol-treated samples show that the low-temperature maxima in the alcohol desorption from the M3+-exchanged clays are due to unchanged alcohol, whilst those occurring at 80°C (t-BuOH), 110°C (i-PrOH) and 160°C (n-PrOH) are due, in the main, to alkene produced from the intramolecular dehydration of the respective alcohol. Changes in the IR spectra of the adsorbed alcohols occur at temperatures which are in accord with the mass spectral data. No mass spectral evidence was found for the formation of dialkylethers via the competing intermolecular process but dimerisation and oligomerisation of t-BuOH were observed.