Acetate intercalated NiAl-Layered Double Hydroxide nanoparticles were prepd. 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 diam. ranging from 47 nm to 2 μm. The anal. of the thermal behavior evidenced that the spherical form was maintained upon calcination up to 1100°, giving rise to derived mixed oxide (NiO + NiAl2O4) nanospheres. The spherical morphol. 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 diam. of 65%. The different materials were characterized using x-ray diffraction, FTIR spectroscopy, scanning and transmission electron microscopies, dynamic light scattering, thermal anal. and nitrogen sorption. [on SciFinder(R)]