A nanosandwich made from Ag nanoparticles (Ag NPs) arrays, the two-dimension single-layer graphene (SG) and metallic Cu contact was constructed for the hydrogen peroxide (H2O2) generation utilizing solar energy without an external bias. The shifting of binding energy towards lower energy in Ag core-level electronic spectrum is an evidence of strong coupling between Ag and graphene, which can efficiently transfer hot-holes from Ag to Cu by a built-in electric field so that the hot-electrons on Ag NPs are directly utilized to initiate the H2O2 generation. This Ag-graphene-Cu nanosandwitch can provide a stable photocurrent of -15.8 mu A cm(-2), a stable photovoltaic voltage of 17.5 mv cm(-2), and a H2O2 yield of 229.33 mu M after 6 h. To understand the mechanism of oxygen reduction reaction (ORR) in Ag-graphene-Cu systems, the electron transfer number for photocatalytic ORE. and the surface facet of Ag NPs were studied. The Ag NPs in Ag-graphene-Cu systems with the deposition time of 180 s clearly shows that an amount of < 200 > facets are distributed on Ag nanoparticle surface, which can catalyze ORR by 2-electron pathway to generate H2O2 efficiently. This novel Ag-graphene-Cu nanosandwitch offers a new transfer path for hot-electrons and potentially provides a new concept for driving efficient solar energy to chemical energy.