Aurivillius nanostructures of Bi2ZnAl2O9 were biosynthesized via a green co-precipitation method using bismuth nitrate pentahydrate, zinc acetate dihydrate and aluminum acetate in the presence of ethanol amine as the precipitating agent and mulberry leaves extract as preparing the green and mild media for the reaction of catalyst synthesis. For better characterization of the obtained nanostructures of Aurivillius, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and field emission scanning electron microscopy (FE-SEM) were applied as the characterizing techniques. In spite of the electrical, physical and photochemical applications of Aurivillius nanostructures, for the first time, perovskite-like Aurivillius nanostructures were used in the organic chemical synthesis of pyrimidines. These recyclable heterogeneous nanoparticles were applied in the one-pot Biginelli coupling reaction of beta-keto esters, different aromatic aldehydes and urea to afford the related 3,4-dihydropyrimidin-2-(1H) derivatives in good to excellent yields under solvent-free conditions at 80C as the optimized temperature