•Green and facile synthesis for rGO/Ag nanocomposites was synthesized.•Mechanism is attributed to the synergistic effect of two hydrolysis products of TD.•First principles prove defect is help for rGO/Ag formation and its conductivity. Recently, graphene decorated with various inorganic nanoparticles, such as Pt, Au, Ag, TiO2 and Fe3O4, among which Ag nanocomposites are good candidates for electronics, optics, electrochemistry and catalysis. However, preparation techniques for Ag nanoparticles/carbon matrix hybrids require tedious multi-step processes often involving toxic reducing agents/high temperatures which is not viable for scalable production. Here, a facile, one step and eco-friendly chemical co-reduction route was utilized to synthesis of a new nanocomposites by Ag nanoparticle anchored on reduced graphene oxide (rGO) at ambient temperature and combined first principles theoretical analyze their interfacial adsorption behavior, is reported. In this way, graphene oxide (GO) and Ag+ simultaneously reduced by thiourea dioxide (TD) without using any additional reduced reactants. Results indicated that GO was successfully reduced to rGO and well-dispersed Ag nanoparticles with sizes of 6–7 nm, anchored on the surface of rGO sheets. Reduction mechanism was attributed to the synergistic effect of its hydrolysis products in aqueous media. The experiment and theoretical calculation results obtained demonstrate this method to be applicable to the synthesis of other metals on rGO sheets in order to improve wettability and interfacial bonding between rGO and metal and may possibly find various forthcoming medicinal, industrial and technological applications.