MNPs‐NHC6H4SO3H as an efficient catalyst was prepared and characterized by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), DLS dynamic light scattering (DLS), and thermogravimetric analysis (TGA) techniques. The catalytic activity of MNPs‐NHC6H4SO3H was investigated in the synthesis of 1,4‐diazepines containing the tetrazole ring via a four‐component reaction under microwave irradiation. The heterogeneous catalyst could be recovered easily and reused six times without significant loss of its catalytic activity. The present work demonstrates the advantages of microwave irradiation‐assisted heterogeneous catalysis in the synthesis of 1,4‐diazepines containing the tetrazole ring, compounds that generate great attention in many applications, particularly in medicinal chemistry and drug discovery.