Boehmite is a natural and environmentally friendly compound. Herein boehmite nanoparticles were primarily synthesized and, then, their surface were modified via 3-choloropropyltrimtoxysilane (CPTMS). Afterwards, a new samarium complex was stabilized on the surface of the modified boehmite nanoparticles (Sm-bis(PYT)@boehmite). The obtained nanoparticles were characterized using thermogravimetric analysis (TGA), energy dispersive X-ray spectroscopy (EDS), Brunauer–Emmett–Teller (BET), wavelength dispersive X-ray spectroscopy (WDX), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), Inductively coupled plasma mass spectrometry (ICP-MS), dynamic light scattering (DLS), and X-ray diffraction (XRD) pattern. Sm-bis(PYT)@boehmite was used as an environmentally friendly, efficient, and organic–inorganic hybrid nanocatalyst in the homoselective synthesis of tetrazoles in polyethylene glycol 400 (PEG-400) as a green solvent. Notably, Sm-bis(PYT)@boehmite is stable and has a heterogeneous nature. Thus, it can be reused for several runs without any re-activation.