Film electrodes prepared from oppositely charged silicate submicroparticles and carbon nanoparticles was applied for selective dopamine sensing. Mesoporous silicate submicroparticles with tetraalkylammonium functionalities were prepared by sol-gel method. They were immobilised on an indium tin oxide film surface together with phenylsulphonated carbon nanoparticles by layer-by-layer method: alternative immersion into their suspensions. As it is shown by scanning electron microscopy the obtained film is composed of silicate submicroparticles covered by carbon nanoparticles. The nanoparticulate film is stable and its electroactive surface is significantly larger than substrate. Accumulation of redox active cations indicates that only fraction charged functionalities of carbon nanoparticles are employed in film formation. The obtained electrode exhibits catalytic properties towards dopamine oxidation and its interferences as ascorbic acid, uric acid and acetaminophen. This allows for selective determination of tenth micromolar concentration of dopamine in the presence of these interferences at milimolar level. The detection limit and linear range were determined to 0.1 × 10⁻⁶ mol dm⁻³ and 0.3-18 × 10⁻⁶ mol dm⁻³ respectively.