In the present work, we studied the effects of Cr on the crystal structures and hydrogen storage properties of ternary alloys, Ti0.7V0.3-xCrx and Ti0.8V0.2-xCrx. Metal-hydrogen interactions were characterised by Thermal Desorption Spectroscopy (TDS) and in situ Synchrotron X-ray diffraction (SR-XRD). All initial alloys crystallise with body-centred cubic (BCC) crystal structures formed as solid solutions of V and Cr in Ti. Upon hydrogenation, the dihydrides (Ti,V,Cr)H-2 with face-centred cubic (FCC) structures are formed. An increase in the Cr content leads to systematic changes in the structure and hydrogenation behaviours. The changes include (a) contraction of the unit cells for the initial alloys and for the corresponding dihydrides; (b) slower hydrogen absorption kinetics and an increase in the incubation period for hydrogenation; (c) a decrease in the thermal stability of the saturated hydrides; and (d) a reduction in the apparent activation energy of hydrogen desorption. In situ SR-XRD and TDS studies of the FCC Ti-V-Cr hydrides indicated that their decomposition consists of five individual desorption events. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.