Ni_xCo_1−x(OH)₂ composite microspheres with uniform sizes are successfully synthesized with the assistance of alkali solution by employing a bimetallic Co–Ni–metal organic framework (Co–Ni–MOF) as both the precursor and the self-sacrificing template. The as-obtained Ni_xCo_1−x(OH)₂ composite demonstrates excellent electrochemical performance, including a high specific capacitance of 1235.9 F g⁻¹ at a current density of 0.5 A g⁻¹, good electrochemical stability, with ∼73% retention of its initial capacitance after 10000 cycles, and a high rate capability; this composite exhibits great application prospects as a novel electrode material for supercapacitors.