Nanoplatelets of metal oxides with interesting porous structure were obtained by thermal treatment of Ni/Al hydrotalcite. Structural and surface properties of the porous oxides were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM and HRTEM), and N2 adsorption–desorption. The electrochemical performance of the electrodes was investigated by cyclic voltammetry, electrochemical impedance spectroscopy and constant current charge–discharge measurements. Ni/Al hydrotalcite calcined at 450 °C (NA-450) displayed a maximum specific capacitance (419.0 F g−1) due to the porous structure with the highest specific surface area (142.3 m2 g−1) and small pore size (4.4 nm). The present study shows the potential of NiO nanoplatelets composite material for electrochemical pseudo-capacitors.