Cobalt aluminium hydrotalcites with different compositions were prepared by a coprecipitation method under low supersaturation conditions. The compounds were characterized by X-ray diffraction (XRD), infrared absorption (IR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and BET surface area measurements. XRD and IR studies revealed that all the compounds are single-phase crystallized under a hydrotalcite-like network. Hydrothermal treatments given to the aged sample increased the crystallinity of the samples. TG studies showed two stages of weight loss, the first due to the removal of interlayer water and the second ascribed to the removal of water molecules from the brucite sheet and CO2 from the interlayer carbonate anion, whose transition temperature depends on the Co/Al atomic ratio. Thermal calcination of these materials results in the formation of high surface area non-stoichiometric spinel phase whose crystallinity increases with increase in the calcination temperature attributed to the sintering of the particles. © 1995 Chapman & Hall.