A simple strategy is presented for the construction of an electrochemical interface with a tunable kinetic barrier by self-assembling organically modified silica gel and gold nanoparticles. Self-assembly of an organically modified silica layer is carried out from the hydrolyzed sol of the precursor mercaptopropyltrimethoxysilane. The kinetic barrier of this self-assembled silicate film is modified by gold nanoparticles that are self-assembled into the silicate network. The electrochemistry of ferricyanide redox reaction is used as a marker to probe the interface.