[en] A new sample preparation method for the water content determination of mulin by volumetric Karl Fischer (KF) titration was developed and compared to the usual method of introducing the sample directly in the methanol-based working medium, modified or not by formamide (1:3, v/v) in order to increase sample solubility. In the proposed method, inulins were externally prepared by dissolving them in pure formamide (2.5:7.5, w/w). The time of analysis of the liquid/liquid reaction of the new method between the dissolved sample and the reaction medium is about 1-2 min, while the usual KF method is stopped after the 10 min delay time. The developed method permits the determination of water included in the crystals of the sample, confirmed by analysing both crystalline and amorphous mulin samples. Another advantage of this new method is its applicability for the water content determination of other polysaccharides that are not readily soluble in the working medium. Moreover. water content determination can be done by any type of volumetric KF titrator, as this proposed technique is not dependent on any additional tools such as a built-in homogeniser or a heatable titration beaker. (c) 2006 Elsevier B.V. All rights reserved.