A cylindrical piece of Au/graphene hydrogel, 1.08 cm in diameter and 1.28 cm in height, has been synthesized through the self-assembly of Au/graphene sheets under hydrothermal conditions for the first time. The hydrogel, containing 2.26 wt% Au, 6.94 wt% graphene, and 90.8 wt% water, exhibited excellent catalytic performance towards the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP), which is about 90 times larger than previously reported values for spongy Au nanoparticles and 14 times more than the highest value among the polymer supported Au nanoparticle catalysts. The high catalytic activity arises from the synergistic effect of graphene: (1) the high adsorption ability of graphene towards 4-NP, providing a high concentration of 4-NP near to the Au nanoparticles on graphene; and (2) electron transfer from graphene to Au nanoparticles, facilitating the uptake of electrons by 4-NP molecules.