Novel optical materials of graphene-Ag nanowire hybrids are fabricated as the substrate for graphene-mediated surface-enhanced Raman scattering (G-SERS). This G-SERS substrate significantly increases probability and efficiency of surface catalytic reaction co-driven by graphene-Ag nanowire hybridization, compared with those reactions individually driven by monolayer graphene or monolayer Ag nanowire. Experimental and theoretical results reveal advantages of G-SERS for the co-driven chemical reactions. Firstly, single layer graphene can efficiently harvest plasmonic hot electrons generated from plasmon decay, and thereby significantly increase the ability of collecting hot electrons. Secondly, lifetime of hot electrons (harvested by the graphene) can be significantly prolonged from femtoseconds to picoseconds, revealed by ultrafast pump-probe transient absorption spectroscopy. These plasmonic hot electrons with larger density and longer lifetime can greatly enhance surface catalytic reaction. Our work not only can reveal the nature of plasmon-graphene co-driven surface catalytic reaction on G-SERS substrate, but also can promote the development of novel optical materials based on plasmonic metal-graphene hybrids.