In this work the results of investigation of mechanism of alloy formation in Ti-Nb system by "Hydride cycle" (HC) method are presented. The temperature regime of dehydrogenation-sintering is defined; the dependences of phase composition of the synthesized alloys on the dispersity and ratio of source reagents (TiH2 and NbHx powders) are studied. X-ray method is used for determination of structural characteristics of synthesized alloys and their hydrides. The results indicate that the crystal lattice and morphology of Ti-Nb alloys are sensitive to the content of Nb: at increasing of NbH portion in the charge, the beta-phase becomes prevailing in the formed BCC alloy. The BCC alloys have been estimated as effective hydrogen storage materials. Therefore, we studied the interaction of synthesized alloys with hydrogen in combustion regime to obtain their hydrides. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.