Two-dimensional inorganic solids, such as layered double hydroxides (LDHs), also defined as anionic clays, have open structures and unique anion-exchange properties which make them very appropriate materials for the immobilization of anions and biomolecules that often bear an overall negative charge. This review aims to describe the important aspects and new developments of electrochemical sensors and biosensors based on LDHs, evidencing the research from our own laboratory and other groups. It is intended to provide an overview of the various types of chemically modified electrodes that have been developed with these 2D layered materials, along with the significant advances made over the last several years. In particular, we report the main methods used for the deposition of LDH films on different substrates, the conductive properties of these materials, the possibility to use them in the development of membranes for potentiometric anion analysis, the early analytical applications of chemically modified electrodes based on the ability of LDHs to preconcentrate redox-active anions and finally the most recent applications exploiting their electrocatalytic properties. Another promising application field of LDHs, when they are employed as host structures for enzymes, is biosensing, which is described considering glucose as an example.
