Amorphous Pd-Au-Si-based metallic glass thin films (MGTFs) obtained by physical vapor deposition were deposited on multilayered graphene (MLGR) supported on Si/SiO2, where the MLGR is carried to the top by upward pressure of the deposited atomic layer passing through the crystal lattice of graphene. Samples were electrochemically hydrogenated by chronoamperometry and characterized by cyclic voltammetry in 0.1 M H2SO4. MLGR-containing samples have prominent Raman peak at 1415 cm1. This sample shows ~2.6 times larger hydrogen desorption charge and ~4.5 times larger electrocatalytic hydrogen activity compared to the MLGR-free counterparts. Furthermore, the capacitance retrieved from the simulation of electrochemical impedance data indicates a ~2.6 times increase upon MLGR inclusion. High-resolution (scanning) transmission electron microscopy after hydrogenation corroborates the existence of nm-sized PdHx crystals around the MGTF – Si/SiO2 interface and the presence of a graphene layer on top of the MGTF due to bond breaking between the MLGR and Si/SiO2. The enhanced hydrogen activity due to the synergistic effect of MLGR and MGTF layer-by-layer nanostructure reveals itself in the diffusion kinetics, where 50% faster hydrogen ion transfer into the MGTF is obtained when the MLGR top layer is present. The areal and volumetric hydrogen desorption charge exceed almost all the considered Pd-based counterparts, especially when comparing systems with similar thicknesses. Hence, the developed hybrid nanostructure can be envisaged as an alternative ultra-high hydrogen charger for small-scale applications.