Abstract A review is presented of the basic principles, theory and instrumentation underlying the observation of ions with the technique of electron stimulated desorption (ESD) and the results of some recent investigations with water adsorbed at metal and semiconductor surfaces are employed to illustrate the state of research in the field. The evolution of theoretical models of desorption from the pioneering work of Redhead, Menzel and Gomer to the present state of theory with considerations of hole-hole interactions are summarised, with particular emphasis on the physical actions involved in the desorption processes. Methods of study of desorbed ions using mass spectrometers, retarding field analysers and time-of-flight techniques are examined, as well as methods for determining the angular distribution of desorbed ions. The response with ESD at the interface formed with water is particularly striking in view of the variety and the range of desorption efficiency of the ions produced. Experimental factors contributing to the possible enhancement of ion production are examined and the results of measurements of desorption parameters are discussed and compared with the predictions of theory.