Aims: We characterise the gas in the extended atmospheres of the oxygen-rich asymptotic giant branch (AGB) stars W Hya and R Dor using high angular resolution ALMA observations. Methods: We report the detection and investigate the properties of high-excitation Λ-doubling line emission of hydroxyl (OH). Results: The OH lines are produced very close to the central stars and seem optically thin and with no maser effect. We analyse the molecular excitation using a population diagram and find rotational temperatures of ˜2500 K and column densities of ˜1019 cm-2 for both sources. For W Hya, we observe emission from vibrationally excited H2O arising from the same region as the OH emission. Moreover, CO v = 1, J = 3 - 2 emission also shows a brightness peak in the same region. Considering optically thin emission and the rotational temperature derived for OH, we find a CO column density ˜15 times higher than that of OH, within an area of (92 × 84) mas2 centred on the OH emission peak. These results should be considered tentative because of the simple methods employed. The observed OH line frequencies differ significantly from the predicted transition frequencies in the literature, and provide the possibility of using OH lines observed in AGB stars to improve the accuracy of the Hamiltonian used for the OH molecule. We predict stronger OH Λ-doubling lines at millimetre wavelengths than those we detected. These lines will be a good probe of shocked gas in the extended atmosphere and are possibly even suitable as probes of the magnetic field in the atmospheres of close-by AGB stars through the Zeeman effect.