Electrodeposition is an “ancient” technique that has been historically used to impart corrosion resistance, to improve frictional wear, and to increase the decorative properties of various materials including those used in automobile parts, integrated circuits, and common household items. Recently, it has also been used as a method to form inorganic and hybrid composite films on conducting surfaces through the electrogeneration of either hydroxide ions or protons in the presence of alkoxysilanes. An increase in pH at the electrode surface through the reduction of oxygen, for example, hydrolyzes the alkoxysilane precursors yielding colloidal particles that coalesce to form the material, typically a thin film. The application of positive potentials to decrease the pH through the oxidation of water at the electrode surface also causes the coalescence of colloidal particles to yield solid oxide structures. In this presentation, electrodeposition as a means to prepare composite materials form organoalkoxysilanes will be discussed.