The synthesis of alumina exhibiting different crystallinities, textures and morphologies is described. The tailoring of amorphous or nanocrystalline alumina forms is effected by the thermochemical decomposition of selected mono- and polynuclear molecular precursors, i.e. aluminum alkoxides. The role of mesostructured alumina is shortly discussed. The growth of alumina whiskers is characterized and the synthesis of single-crystalline alumina, i.e. industrial alumina, sapphire and ruby, is mentioned. The various processes and products are characterized by means of thermoanalytical and spectroscopic techniques, X-ray diffractometry and electron microscopy.