Hydrogen storage performance of the TiFe-based materials suffers from difficulties with hydrogenation and sensitivity towards impurities in hydrogen gas reducing hydrogen uptake rates and decreasing the cycle stability. In present work the surface modification of the sintered Ti 1.1Fe 0.9O x and arc-melted TiFe was performed using autocatalytic deposition of the Pd-based catalytic layers in order to achieve improvement of the H storage characteristics. Pd deposition proved to be efficient in significant facilitation of the hydrogenation ability of the materials at moderate H 2 pressures and room temperature, even after their long exposure to air. Activation performance of the sintered Ti 1.1Fe 0.9O x is superior than that for the arc-melted TiFe. This effect was associated with the presence of the oxygen-containing suboxide Ti 4Fe 2O 1− x in the sintered sample acting as a hydrogen transfer catalyst. γ-Aminopropyltriethoxysilane pre-functionalization and subsequent Pd–P autocatalytic deposition onto the sintered Ti 1.1Fe 0.9O x intermetallic substrate resulted in a better hydrogenation kinetics compared to the samples prepared by the conventional Pd deposition.