The hydrothermal method was mostly used for the preparation of metallic double hydroxides. However, it is very time-consuming and energy-consuming. In this study, we for the first time reported a facile, rapid and cost-effective microwave strategy to fabricate nickel/cobalt double hydroxides (Ni/Co-DH). Four solvents, including water, ethanol, isopropanol and tertbutanol, were used for the synthesis of Ni/Co-DH to examine effect of the reaction medium. The study demonstrated that the Ni/Co-DH prepared in the aqueous solution exists as the mixture of α-Ni(OH)2 and β-Co(OH)2. However, the Ni/Co-DH prepared in the organic solvent studied has a hydrotalcite-like structure. Moreover, the Ni/Co-DH prepared in ethanol offers ultrathin flowercluster structure with a three-dimensional morphology. Owing to the greatly improved Faradaic redox reaction and mass transfer, the Ni/Co-DH electrode exhibits excellent pseudocapacitance performance, including high specific capacitance and rate capability, good charge/discharge stability and long-term cycling life. Its maximum specific capacitance was up to 1887.5Fg−1 at the current density of 1Ag−1, which is more than 2.4-fold that of the Ni/Co-DH prepared in the aqueous solution. The specific capacitance can remain 1187.5Fg−1 when the current density increases to 10Ag−1. The capacitance can keep at least 99.7% at the current density of 8Ag−1 after 3000 cycles. This work also provides a promising approach for the synthesis of various metallic double hydroxide materials with largely enhanced supercapacitor behavior, which can be potentially applied in energy storage/conversion devices.