Porous nickel cathode was protected by potentiostatically deposited cobalt at different experimental conditions: oxidation potential and electrolysis duration. The deposition growth increased with the oxidation potential yielding a more developed granular structure with smaller grains. Thin layers of Co 3 O 4 were identified by X-ray diffraction (XRD) and Raman spectroscopy. CoOOH was detected by X-ray photoelectron spectroscopy (XPS) before annealing treatment and Co 3 O 4 after heating the sample at 500°C during 4h in air. After this treatment, some morphological changes were observed on the coated samples due to grain compaction and oxidation of the nickel substrate. The porosity of the coated samples was relatively close to that of the sole porous nickel. These coatings exhibited an appropriate dual-pore structure with macro and micro pores, a basic MCFC requirement.