Thiol-functionalized　reduced　graphene　oxide　(SRG)　was　prepared　by　coupling　the　carboxyl　groups　on　the　pre-carboxyl-functionalized　graphene　oxide　(GO)　with　cysteamines　through　amide　bonds.　The　as-prepared　SRG　can　function　both　as　a　support　and　reducing　agent　for　the　formation　of　Au/SRG　nanohybrids　with　evenly　distributed　Au　nanoparticles　on　RGO.　The　thiol　linkage　on　the　RGO　can　act　as　anchor　for　Au　nanoparticles　and　due　to　the　existence　of　the　strong　interaction　between　them,　the　agglomeration　of　Au　nanoparticles　can　be　significantly　impeded.　The　step-by-step　assembly　process　of　the　Au/SRG　nanohybrid　was　monitored　and　the　products　obtained　were　characterized　by　Fourier　transform　infrared　spectroscopy　(FT-IR),　Raman　spectroscopy,　X-ray　photoelectron　spectroscopy　(XPS),　X-ray　absorption　near-edge　spectroscopy　(XANES),　atomic　force　microscopy　(AFM),　powder　X-ray　diffraction　(XRD),　transmission　electron　microscopy　(TEM)　and　high-resolution　transmission　electron　microscopy　(HRTEM).　The　as-prepared　Au/SRG　nanohybrid　showed　superior　catalytic　performance　for　the　hydrogenation　of　4-nitrophenol　(4-NP)　to　4-aminophenol　(4-AP).　It　is　expected　that　the　method　for　the　preparation　of　the　Au/SRG　nanohybrids　can　also　be　applied　to　the　preparations　of　other　RGO-based　nanohybrid　materials　which　may　find　a　variety　of　interesting　applications.　©　2014　The　Royal　Society　of　Chemistry.