The three-dimensional and porous structure of nickel foam makes it an attractive material for employment in cost-effective electrochemical supercapacitors. This communication presents ac. impedance spectroscopy and cyclic voltammetry electrochemical examinations of potential supercapacitor electrode materials, fabricated by means of simple electrochemical procedures, employed to as-received Ni foam material. This involves the electro-oxidation and Co-catalytic modifications of baseline nickel foam samples. Hence, the supercapacitor-type performance (as evidenced over the examined potential range in 0.1 M NaOH solution) of base nickel foam material could extensively be tailored by means of simple surface and catalytic refinements. The latter was evidenced through the employment of combined electrochemical (cyclic voltammetry, ac. impedance) and SEM/EDX (Scanning Electron Microscopy/Energy Dispersive X-Ray) surface spectroscopy evaluations.