The compositional window in Nb-Ni-Ti alloys leading to the crystallization of primary alpha-Nb phase and the eutectic (alpha-Nb + NiTi) phase is of high technical relevance due to its favorable properties with respect to hydrogen permeation. The solidification behavior of Nb-Ni-Ti alloys in the primary alpha-Nb phase region is investigated to reveal the potential solidification paths. The study is based on the characterization of as-cast microstructures in combination with numerical calculations of solidification paths using the CALPHAD method coupled with a microsegregation model. Four different kinds of solidification paths depending on initial composition and cooling rate are found. Correspondingly, a new compositional window appropriate for hydrogen permeation is established in the primary alpha-Nb phase region. The variation of the hydrogen permeability of the alloys in this window is surprisingly high. High Nb content and Ni/Ti ratio lead to a high permeability. Nb55Ni20Ti25 shows the highest permeability at 673 K, particularly 2.9 x 10(-8) mol H-2 m(-1) s(-1)Pa(1/2). This is about 1.8 times higher than that of pure Pd. Crown Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.