In this work, the novel bifunctional nanosized ionic liquid catalyst [4,4′-bipyridine]-1,1′-diium trinitromethanide (BPDTNM) was designed, synthesized, and characterized by using FT-IR spectra, ¹H and ¹³C NMR spectra, X-ray diffraction patterns (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), thermogravimetry (TG), derivative thermogravimetry (DTG) analysis, differential thermal analysis (DTA), and HPLC-mass spectroscopy. The synthesized nanosized catalyst was successfully applied to the synthesis of 1-(benzoimidazolylamino)methyl-2-naphthol derivatives via a straightforward one-pot three-component condensation reaction of 2-aminobenzimidazole, 2-naphthol, and a wide range of aromatic aldehydes under mild and solvent-free conditions.