An order–disorder transition occurs in 1-adamantanol at 359 K on heating and at 342 K on cooling, with transition entropies of 36 and 34 J K−1 mol−1, respectively. FT-ir spectra show that free hydroxyl groups exist in the high temperature phase, but the majority of the O—H groups remain hydrogen bonded. The barrier to adamantyl group rotation in the low-temperature phase, determined from proton spin–lattice relaxation time measurements, is 20.9 Kj mol−1, and the barrier to rotation in the high-temperature phase is 35.0 kJ mol−1.