Reduced graphene oxide/carbon nanotube/α-Ni(OH)2 (RGO/CNT/α-Ni(OH)2) composites are successfully synthesized by a one-pot hydrothermal route. The structural characterization of the composites by EDX, XRD, FT-IR, XPS, Raman, FESEM and TEM indicate that α-Ni(OH)2 nanoparticles with the size around 5 nm are randomly decorated onto three-dimensional (3D) hierarchical structure RGO/CNT. The electrochemical performances of the composites are evaluated by cyclic voltammogram, galvanostatic charge–discharge and electrochemical impedance spectroscopy. Interestingly, it is found that the electrochemical capacitance of the composites depends on the amount of CNTs to a large extent and RGO/CNT/α-Ni(OH)2 composite (GC2Ni2) with optimized ratio exhibits the high specific capacitance of 1320 F g−1 at 6 A g−1. In addition, the cycling measurements show that GC2Ni2 maintains a specific capacitance of 1008 F g−1 at 15 A g−1 after 1000 cycles corresponding to a reduction of capacitance of about 7.8%. The enhancement in specific capacitance and cycling stability is believed to be due to the 3D RGO/CNT conductive network which promotes not only efficient charge transport and facilitates the electrolyte diffusion, but also prevents effectively the volume expansion/contraction and aggregation of electroactive materials during charge–discharge process.