A series of N,N′-alkylidene bisamides were prepared via a green and environmentally friendly synthetic protocol from the reaction of phenyl acetylene or hex-1-yne, aromatic aldehyde, and benzamide or acetamide. Silica-supported barium chloride (SiO2–BaCl2) catalyzes the process of the reaction. The prepared catalysts were characterized by X-ray diffraction, and the products were obtained with high conversions and yields.