Sol‐gel‐derived silica thin films generated onto electrode surfaces in the form of organic‐inorganic hybrid coatings or other composite layers have found tremendous interest for being used as platforms for the development of electrochemical sensors and biosensors. After a brief description of the strategies applied to prepare such materials, and their interest as electrode modifier, this review will summarize the major advances made so far with composite silica‐based films in electroanalysis. It will primarily focus on electrochemical sensors involving both non‐ordered composite films and vertically oriented mesoporous membranes, the biosensors exploiting the concept of sol‐gel bioencapsulation on electrode, the spectroelectrochemical sensors, and some others.