The isolation and characterisation of marine dissolved organic matter (DOM) are still not readily achieved today. The study of this chemically complex material is particularly difficult, especially as it is hindered by the high salinity of seawater. It is therefore essential to develop a method in which a sufficient quantity of marine organic matter can be collected for structural analyses. Reverse osmosis (RO) is often used for the concentration of DOM from freshwaters, due to the fact that DOM is not modified during RO and that DOC recoveries are high (about 80%). Unfortunately, RO cannot be used directly to isolate marine DOM, since both salts and organic matter are concentrated during the process. Therefore, marine samples have to be desalted before their concentration by RO. Our aim was to develop a desalting step of seawater by electrodialysis (ED), whilst minimising DOM modifications and losses. The process was first developed with small volumes (2 C) of artificial and Mediterranean seawater and was then applied to larger volumes. We showed that 20 L of Mediterranean seawater could be rapidly desalted (in less than 7 h) and, by monitoring the quality of DOM in desalted subsamples collected during ED using spectrofluorometry, that the quality of DOM was not significantly modified. It was concluded that desalted samples were still representative of the initial seawater samples. It should be noted, however, that care has to be taken in choosing the ratio of the volume of water to be desalted over the membrane surface area in order to limit DOM modifications and losses. Electrodialysis efficiently removed up to 75% of the salts present in the seawater samples whilst recovering most of unaltered DOM. ED and RO could then be combined in order to isolate, concentrate and characterise marine organic matter. (C) 2008 Elsevier B.V. All rights reserved.