The BiFeO3 perovskite-type oxide was synthesized using the citrate gel method and the catalytic activity of the BiFeO3 was assessed in a multicomponent reaction of benzil, an aromatic aldehyde, and an amine in the presence of ammonium acetate under solvent-free conditions. The physical and chemical properties of the catalyst were determined using X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and Energy dispersive X-ray spectroscopy and Imidazole products were identified by comparing their melting points with already reported papers. SEM illustrated a smooth surface with a uniform morphology for the catalyst. Meanwhile, XRD indicates two phases of BiFeO3 and Bi2Fe4O9 at the same time. Moreover, IR and EDS both showed the absence of any impurities in the mentioned catalyst. The experimental data revealed excellent catalytic performance for BiFeO3 in absence of any solvents. Therefore, BiFeO3 can be used as an efficient and green catalyst for the synthesis of 1,2,4,5-tetrasubstituted Imidazoles.