Graphene oxide/polyamidoamine dendrimers (GO/PAMAMs) composites were used to remove Cr(VI) from simulated effluents, the adsorption kinetics and thermodynamics of Cr(VI) onto GO/PAMAMs were systematically investigated. The results showed that the optimum pH value was 2.5, the removal percentage reached 90.7% for 30 mg/L of Cr(VI) within 120 min. The adsorption process was well described by pseudo-second-order kinetic model. The maximum adsorption capacities of Cr(VI) onto GO/PAMAMs were found to be 131.58, 183.82 and 211.42 mg/g at 293.15, 303.15 and 313.15 K, respectively, which were calculated from the Langmuir model equation. The adsorption thermodynamic parameters indicate that the adsorption of Cr(VI) onto GO/PAMAMs is a spontaneous endothermic process. The XPS analysis reveals the adsorption and removal mechanism of Cr(VI) on GO/PAMAMs that first the Cr(VI) binds to the protonated amine of GO/PAMAMs, then Cr(VI) be reduced to Cr(III) with the assistance of π-electrons on the carbocyclic six-membered ring of GO in GO/PAMAMs, and then Cr(III) was released into solution under the electrostatic repulsion between the Cr(III) and the protonated amine groups.