The deuterium thermal desorption of various YFe2Dx (x = 1.3, 2.5, 3.5, 4.2) compounds has been studied using differential scanning calorimetry (DSC) and thermal desorption (TD) experiments. These studies show that the number of desorption peaks increases with the deuterium content. In order to understand the origin of this multipeak behaviour, in situ neutron diffraction experiments during thermal desorption have been performed from 290 K to 680 K on YFe2D4.2. Upon heating, a multipeak TD spectrum is observed. It relates to the existence of several YFe2Dx phases with different stabilities. The rate limiting step of this thermal desorption has been therefore attributed to several successive phase transformations rather than to different types of interstitial sites as proposed in previous TD models reported for C15-Laves phase compounds. (C) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.