Electrochemically assisted deposition of an ormosil film at a potential where hydrogen ion is generated as the catalyst yields insulating films on electrodes. When the base electrode is modified with 20-nm poly (styrene sulfonate), PSS, beads bound to the surface with 3-aminopropyltriethoxysilane (APTES), and using (CH3) 3SiOCH3 as the precursor, the resulting film of organically modified silica (ormosil) has cylindrical channels that reflect both the diameter of the PSS and the distribution of the APTES-PSS on the electrode. At an electrode modified by a 20-min immersion in 0.5 mmol dm−3 APTES followed by a 30-s immersion in PSS, a 20-min electrolysis at 1.5 V in acidified (CH3) 3SiOCH3 resulted in an ormosil film with 20-nm pores separated by 100 nm. Cyclic voltammetry of Ru (CN) 6 4− at scan rates above 5 mV s−1 yielded currents controlled primarily by linear diffusion. Below 5 mV s−1, convection rather than the expected factor, radial diffusion, apparently limited the current.