The implications of organically-modified silica-based materials in electrochemical science is reviewed along with some selected recent trends in the field of functionalized and sol–gel silica electrochemistry. These recent trends include the electro-assisted generation of organosilica films on solid electrode surfaces, the preparation and applications of sol–gel derived composite (carbon, gold, nanotubes) electrodes, the electrochemical characterisation of mass transfer reactions in porous functionalized silicas, solid-state electrochemistry and gas sensors involving sol–gel materials, imprinted functionalized silica, and the electrochemical characterisation and applications of ordered mesoporous organosilicas.