Acetate intercalated NiAl-Layered Double Hydroxide nanoparticles were prepared by polyol process and further used as building blocks to form hybrid LDH spheres by a spray drying technique. The spherical aggregated LDH particles display a polydispersed size with a diameter ranging from 47 nm to 2 mu m. The analysis of the thermal behavior evidenced that the spherical form was maintained upon calcination up to 1100 degrees C, giving rise to derived mixed oxide (NiO + NiAl2O4) nanospheres. Interestingly, the spherical morphology of the LDH materials was also retained during anion exchange process. The replacement of the intercalated acetate anion by of a voluminous anion such as dodecylsulfate induces an increase of the nanosphere mean diameter of 65%. The different materials were deeply characterized using X-ray diffraction, FTIR spectroscopy, scanning and transmission electron microscopies, dynamic light scattering, thermal analysis and nitrogen sorption. (C) 2011 Elsevier Inc. All rights reserved.