In this work, the synthesis and characterization of thiol functionalized reduced graphene oxide (TrGO) as a novel base material for the generation of graphene-nanoparticle hybrid materials is reported. TrGO was directly synthesized by refluxing graphene oxide (GO) with phosphorus pentasulfide (P₄S₁₀). The introduction of sulfur containing chemical groups and the partial reduction of GO to TrGO were proven by UV–Vis, XPS and FTIR spectroscopy. CdSe nanocrystal-TrGO (CdSe-TrGO) as well as silver nanoparticle-TrGO (Ag-TrGO) hybrid materials are achieved by attachment of the respective nanoparticles to the thiol groups of the graphene using self-assembly decoration. The resulting hybrid materials were investigated by TEM and photoluminescence quenching experiments.