Mesoporous silica thin films (MCM-41) functionalized with ethylenediamine groups were electrochemically fabricated on electrode surfaces. These ligand functionalized film were a promising matrix for the immobilization of cobalt ions and preparation of cobalt complexes covalently bound to the MCM-41 support. The constructed MCM-41 were characterized by TEM, EDS and TGA analysis. This method yields uniform thin films with hexagonal mesochannels aligned and accessible to electrode surface. Well-defined electrode responses were, therefore, observed for the anchored complexes which made the electrochemical analysis of the structure possible as well. Voltammetric studies revealed the reactivity of the covalently bound complexes differed significantly from the dissolved ones. The anchored complexes preferred to be in their oxidized form which inhibits formation of oxygen adducts. The covalently bound complexes had relatively good leaching stability with good catalytic performance towards hydrogen peroxide reduction.