An electrode structure of a fuel cell for power generation comprises an anodic structure, a cathodic structure, and an ionic exchange membrane disposed between the anodic and cathodic structures. The anodic and cathodic structures respectively are formed by multi-layer structures, to reduce the fuel crossover from the anodic structure to the cathodic structure, to reduce the catalysts applied amount, and to increase an output electrical energy of the fuel cell. The multi-layer structure of the anodic structure comprises a thin platinum alloy black layer, a Pt alloy layer disposed on the carbon material, and a substrate.