The surface oxidation behavior of LiBH4 and NaBH4 was investigated in view of the formation and structure of the surface oxidation and its effect on the hydrogen desorption kinetics. The sample surfaces were intentionally modified by exposure to oxygen in the pressure range from 10 -10 mbar up to 200 mbar. The induced surface changes were systematically studied by means of X-ray photoelectron spectroscopy. NaBH 4 shows a low reactivity with oxygen, while LiBH4 oxidizes rapidly, accompanied by surface segregation of Li. The hydrogen desorption kinetics of LiBH4 were studied by thermal desorption spectroscopy with particular emphasis on the analysis of the desorbed gases, i.e. diborane and hydrogen. The surface oxidation induces the formation of a Li2O layer on LiBH4, significantly reduces the desorption of diborane, and enhances the rate of hydrogen desorption. © 2010 the Owner Societies.