New layered solids by the combinatorial stacking of different atomic layers are emanating as novel candidates for energy efficient devices. Here, sequentially stacked single layer graphene-molybdenum disulfide (MoS2) van der Waals (vdW) solids are demonstrated for their efficacy in the catalysis of hydrogen evolution reaction (HER), and importance of their stacking order in tuning the photo-electrocatalytic (PEC) efficiency is unraveled. Single layer graphene and a few layered MoS2 stacked vdW solids based transparent flexible electrodes were prepared, and a particular stacking sequence where top-graphene: bottom-MoS2/polydimethylsiloxane (PDMS) geometry (MSGR) exhibited the lowest onset and over potentials and a very high exchange current density (j 0 ∼ 245 ± 1 μA cm-2) in acidic HER in comparison to the individual layers and other stacked configuration (MoS2 on top of graphene on PDMS, GRMS). The HER studies under dark and white light illuminations were conducted to explore the PEC responses of the devices. The augmented HER performance of MSGR is further confirmed from the charge transfer resistance measurements using electrochemical impedance spectroscopy. Role of graphene plasmonics and MoS2 to graphene electron transfer were studied, and this study unravels the importance of a new factor, stacking order of vdW layers, while designing novel devices from the layered solids.