The electrochemical behavior of layered double hydroxides (LDHs) containing 3d metal is presented here by analyzing the recent research progress described in the literature. Electron transfer within these inorganic lamellar materials can be promoted by redox-active cation sites (nickel, cobalt, iron, or manganese) located within the layer structure, with a potential window varying between −0.1 and 0.8 V/SCE in aqueous electrolyte, depending on the nature of metal cations and on the LDH composition. Additives, such as metal complexes, metal oxides, or nanocarbons to form hybrid or composite LDH-based materials, can further improve these redox properties. The electrochemical behavior of those LDH materials and their hybrid derivatives and composites, investigated mainly by cyclic voltammetry and electrochemical impedance spectroscopy, is described. A special attention is paid on NiAl-LDH and CoAl-LDH, as illustrative examples of LDH electrochemistry.