Ternary alloys of general composition (TiFe)(100-x)M-x (M = Co, Nb) have been synthesized from pure metals through high-energy ball milling. The maximum concentration of alloying components allowing formation of single phase TiFe-type compounds has been defined as 2 at.%. The hydrogenation behavior of the mechanical alloys in comparison with the arc-melted ones of the same composition has been studied by a combination of volumetric and calorimetric techniques. Influence of the alloy composition and the synthesis mode on the crystal structure of TiFe and its hydrides has been evaluated. It has been shown that the thermochemical method based on calorimetric titration provides more accurate information about phase transformations in the nanocrystalline metal hydride systems. The obtained results show that the third components slightly affect the hydrogen storage performance of non-equilibrium mechanical alloys in contrast with alloys produced by conventional melting. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.