Urchin-like Ni(OH)2–Co(OH)2 hollow microspheres were successfully synthesized by a microwave-incorporated hydrothermal method. The Ni(OH)2–Co(OH)2 hollow microspheres achieved a high specific capacitance of 2164Fg−1 at 1Ag−1 and long-term cycle life. Electrochemical data reveal that the Ni(OH)2–Co(OH)2 hollow microspheres exhibits much better electrochemical reversibility and specific capacitance retention than that of the single Ni(OH)2 or Co(OH)2 based on peak potential difference, symmetry of charge–discharge curves, and specific capacitances at high charge–discharge rates. Furthermore, the designed Ni(OH)2–Co(OH)2/graphene asymmetric supercapacitor displays good reversibility and a high specific capacitance of 169Fg−1 at 1Ag−1, 145Fg−1 at 3Ag−1, and 116Fg−1 at 5Ag−1, indicating a good ability to deliver a high energy density at a high power density. These results proved that the Ni(OH)2–Co(OH)2 hollow microspheres can be promising electroactive materials for supercapacitor and the microwave-incorporated hydrothermal method provided a one-step, template-free, and cost-effective route for fabricating pseudocapacitive materials in 3-D form.