The crystal structure, microstructure, hydrogen storage properties and thermal stability of the as-cast and annealed V35Ti20Cr45 alloys prepared by arc-melting were studied in this work. It was confirmed that the as-cast alloy is a body-centered cubic (bcc) single phase, while it consists of bcc main phase and C14-typed Laves secondary phase after annealed at 973 K for 72 h. As a result of the microstructure change, the activation performance and kinetic properties of the annealed alloy are improved greatly due to the catalysis of C14-typed Laves secondary phase in the annealed alloy. The kinetic mechanism of hydrogen absorption/desorption processes in the as-cast and annealed alloys was discussed using the Johnson-Mehl-Avrami (JMA) equation. Based on the plateau pressure data from pressure-composition-temperature (PCT) measurements with the Vent Hoff equation, the calculated formation enthalpies of the hydride formed in the as-cast and annealed alloys indicate that heat treatment results in lower thermal stability of the hydride in the as-cast alloy. Furthermore, using the Kissinger method with the peak temperatures from differential scanning calorimeter (DSC) measurements at different heating rates, the calculated activation energies of the dehydrogenation in the as-cast and annealed alloys suggest that heat treatment is very beneficial to improve hydrogen absorption/desorption capacities in the alloy. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.