A novel nanostructured heterogeneous catalyst, namely silica-bonded 1,4-diaza-bicyclo[2.2.2]octane-sulfonic acid chloride (SBDBSAC), has been synthesized and fully characterized by several techniques, including Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermal gravimetric analysis (TGA), differential thermal gravimetric (DTG), scanning electron microscope (SEM), and energy dispersive X-ray analysis (EDX). Afterward, the nanostructured catalyst was utilized as an efficient catalyst for the synthesis of bis-coumarin derivatives by the condensation reaction of arylaldehydes with 4-hydroxycoumarin at 70 °C under solvent-free conditions.