In this work, a hierarchical hybrid structure of reduced graphene oxide (rGO) supported ultrathin α-Ni(OH)2 nanosheets (denoted as α-Ni(OH)2@rGO NSs) has been developed successfully via an environmentally friendly one-step solution method. The resulting product of α-Ni(OH)2@rGO NSs was further characterized by scanning electron microscope, transmission electron microscope, x-ray diffraction, Raman spectroscopy, x-ray photoelectron spectroscopy, and Brunauer-Emmett-Teller. The ultrathin α-Ni(OH)2 nanosheets of around 6 nm in thickness are uprightly coated on the double sides of rGO substrate. When evaluated as electrodes for supercapacitors, the hybrid α-Ni(OH)2@rGO NSs demonstrate excellent supercapacitor performance and cycling stability, compared with the self-aggregated α-Ni(OH)2 powder. Even after 2000 cycles, the hybrid electrodes still can deliver a specific capacitance of 1300 F g(-1) at the current density of 5 A g(-1), corresponding to no capacity loss of the initial cycle. Such excellent electrochemical performance should be attributed to the ultrathin, free-standing, and hierarchical nanosheets of α-Ni(OH)2, which not only promote efficient charge transport and facilitate the electrolyte diffusion, but also prevent aggregation of electro-active materials effectively during the charge-discharge process.