Pd-Based amorphous alloys can be used for hydrogen energy-related applications owing to their excellent sorption capacities. In this study, the sorption behaviour of dc magnetron-sputtered and chronoamperometrically-saturated Pd-Si-Cu metallic-glass (MG) nanofilms is investigated by means of aberration-corrected high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy, and electrochemical techniques. The volume expansion of ΔV = 10.09 Å3 of a palladium hydride unit cell obtained from HRTEM images due to the hydrogenation of the Pd-MG nanofilms is 1.65 times larger than ΔV of the Pd-polycrystalline counterpart loaded under the same conditions. Determined by scanning transmission electron microscopy-high annular dark-field imaging and electron energy loss spectroscopy, the huge difference between the two Pd-based systems is accounted for by the "nanobubbles" originating from hydrogenation, which generate active sites for the formation and expansion of spatially dispersed palladium hydride nanocrystals. A remarkable difference in the hydrogen sorption capacity is measured by electrochemical impedance spectroscopy compared to the Pd polycrystal nanofilms particularly in the α and β regions, where the maximum hydrogen to palladium ratio obtained from a combination of chronoamperometry and cyclic voltammetry is 1.56 and 0.61 for the MG and Pd-polycrystal nanofilms, respectively. The findings place Pd-MGs among suitable material candidates for future energy systems.