Hexagonal normal spinels of nano-nickel aluminate (NiAl 2 O 4 ) have been successfully synthesized through a greener microwave assisted technique using urea as a base. The structure and morphology of synthesized nanomaterials were examined by Powder X-ray Diffraction (PXRD), Field Gun Emissions-Scanning Electron Microscopy (FEG-SEM), Transmission Electron Microscopy (TEM), Brunauer-Emmett-Teller (BET) surface area, Thermogravimetric Analysis (TGA) and Infrared spectroscopic (IR) analysis, which show the polycrystalline asymmetrical nanoparticles ranging in between 10-100 nm with the higher surface area and thermal stability. Furthermore, to explore the potential of nano-nickel aluminate, we used synthesized nanomaterials as a heterogeneous catalyst for the acetylation of alcohols, phenols and amines. Here, we have developed the greener, efficient, economical and recyclable protocol for acetylation reactions. The nano nickel aluminate shows the good catalytic efficiency for solvent free acetylation of amines, while it exhibits moderate catalytic efficiency in case of alcohols and phenols.