Recently, the field of highly-ordered mesoporous and macroporous thin films coated onto solid electrode surfaces has begun to receive attention due to their great interest for electrochemical analysis. This review highlights the features of both electricallyconducting and non-conducting organized layers, which are applicable to designing electrochemical sensors, and the methods applied to construct these novel nanomaterials. We emphasize methods based on use of self-assembled colloidal templates (e.g., surfactants or nanoparticles), around which the materials of interest are formed. We then describe their basic electrochemical behavior and discuss their possible use as electrochemical sensors and biosensors, mostly in the particular case of structured metallic layers, functionalized mesoporous silica films, and some other continuous three-dimensional ordered porous structures.