Mesoporous binary nickel–cobalt (Ni–Co) oxy-hydroxides have been obtained through the microwave-assisted hydrothermal annealing (MAHA) method. The porosity control of the nanostructured Ni–Co oxy-hydroxide nanoparticles is achieved through adding the pluronic triblock copolymer F127 as the surfactant. The structural and electrochemical properties of porous Ni–Co oxy-hydroxide nanostructures are characterized by means of X-ray diffraction (XRD), Brumauer–Emmett–Teller (BET) analysis, transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and cyclic voltammetry (CV). The electrochemical measurement demonstrates that the Ni–Co oxy-hydroxides calcined at 200°C are able to deliver a specific capacitance of 636Fg−1 in 1M NaOH, suggesting their high potential as a novel electrode material of pseudocapacitors with good electrochemical reversibility. In the asymmetric supercapacitor test, the positive electrode is Ni–Co oxy-hydroxide and negative electrode is activated carbon. The specific energy and power, measured at 2Ag−1, for this asymmetric combination are equal to ca. 17Whkg−1 and 1.6kWkg−1, respectively.