Abstract: The α–phase metal hydroxides are layered materials whose structure is similar to that of the better studied layered hydroxides, LDHs. They also have positively charged layers formed solely with divalent cations within brucite-like sheets. These layered hydroxides are important materials owing to their ability to intercalate or ion-exchange various functional anions. This leads to the production of the materials with new physico-chemical properties for use in diverse technological areas, such as catalyses, electrochemical performances, controlled release systems, polymeric nanocomposites, etc. Moreover, αLHs and their nanohybrids have been suitable precursors to make undoped and doped nanostructured metal oxides, metal and metal alloys as well as carbon materials and metal oxide carbon composites.