Metal ions (Al3+ and Co2+) co-doped α-Ni(OH)2/graphene hybrid materials had been successfully synthesized by a facile chemical co-precipitation route. X-ray diffraction (XRD) patterns revealed the successful phase transmission from β-Ni(OH)2 to α-Ni(OH)2 after Al3+ doping and the continuously enlarged interlayer distance of α-Ni(OH)2 after subsequent Co2+ doping. Due to its large interlayer distance, mesoporous structure and highly conductively graphene (GNS), the as-obtained Al-Co co-doped α-Ni(OH)2/GNS composite (Al-Co-Ni/GNS) showed an ultrahigh specific capacitance of 2257 F g−1 at 2mV s−1 as well as good cycling stability with 77% of the initial capacitance retention after 1000 cycles in 6M KOH aqueous solution.