A comprehensive overview is presented on the implication of silica-based organic−inorganic
hybrid materials in electrochemical science. It involves composite materials of both class I
(weak bonds between the organic and inorganic components) and class II (strong chemical
bonds). Starting with a description of the common designs of electrodes modified with these
hybrids, the review then reports their applications in the various fields of electrochemistry,
illustrating the diversity of the organically modified silicates used for this purpose. The mild
chemical conditions allowed by the sol−gel process provide very versatile access to these
electrochemical devices. They have found many applications in electroanalysis, including
preconcentration associated with voltammetric detection, permselective coatings, electrochemical sensors, electrocatalysis, and detectors for chromatography. They were also applied
as redox and conducting polymers, as solid polymer electrolytes for batteries, for the design
of spectroelectrochemical and electro-chemiluminescence devices, and in the field of
electrochemical biosensors.