We have studied the dehydrogenation properties of pure and Ti-doped Na3AlH6 surfaces using density functional theory. For the clean surface dehydrogenation is a multistep process, and involves the desorption of AlH4 complexes which disrupt the structure of the surface. By doping the system with Ti, we found that the segregation energy of Ti is negative, therefore favoring localization of the impurity to the surface of Na3AlH6. Here Ti doping is shown to kinetically favor H-2 desorption, by reducing the energy barrier that the molecule needs to climb to leave the surface. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.