A novel heterogeneous alumina supported silver nanocatalyst (Ag@Al2O3) has been designed and it showed excellent catalytic activity for the N-alkylation of hetero (aromatic) amines and aromatic amines with alcohols as the alkylating agent. Display omitted We have successfully embedded rhombohedral crystallites of silver nanoparticles (Ag-NPs) over mesoporous alumina (Ag@Al2O3) material for the first time. The Ag@Al2O3 has been characterized by powder X-ray diffraction (PXRD), ultra high resolution transmission electron microscopy (UHR-TEM), scanning electron microscopy (SEM), N2 adsorption/desorption isotherm, Fourier transform infrared spectroscopy (FT-IR), ultraviolet–visible absorption spectra (UV–Vis), and thermogravimetric analysis (TGA). The PXRD confirms the presence of the rhombohedral phase of Ag nanoparticles. The agglomeration of the silver nanoparticle having a dimension of 80–90nmhas been clearly observed from UHR-TEM images. This novel nanocatalyst showed excellent catalytic activity towards the N-alkylation of hetero (aromatic) amines and aromatic amines using alcohols as the alkylating agent. The catalyst is heterogeneous in nature and can be recovered and recycled more than five reaction cycles without any noticeable loss in its catalytic activity.