This work demonstrates the use of self-assembled carbon films in designing fuel cell electrode. Well-dispersed mesoporous carbon particles were prepared based on the spontaneous and strong chemisorption of polyoxometalate (POM) solution on carbon surface. Electrostatically self-assembled films of the POM stabilized carbon interlaced with cationic polyelectrolyte binding layer were useful for confining electrodeposition of platinum (Pt) catalyst. The structure and morphology of the resulting films were characterized by X-ray diffraction and scanning electron microscopy respectively. The electrocatalytic activities of Pt deposited on the self-assembled carbon films toward the degradation of small organic molecules are largely dependent on the quantity of Pt and carbon. This work represents a simply controlled test-bed for fundamental studies on loading metal catalysts on ordered mesoporous carbon films for catalysis. (C) 2009 Elsevier B.V. All rights reserved.