A barium-containing crown ether bridged chiral heterotrinuclear salen Zn(II) complex BaZn 2 L(ClO 4 ) 2 , where L is a folded dinuclear chiral (R,R)-salen ligand, has been synthesized and characterized by elemental analysis, 1 H NMR, UV–vis, IR, circular dichroism (CD) spectra, and mass spectra. As a folded dinuclear chiral host, its recognition with achiral guests (imidazole derivatives), rigid bidentate guest (1,4-diazobicyclo[2,2,2]octane, DABCO) and chiral guests (amino acid methyl esters) was investigated by means of UV–vis spectrophotometric titration, CD spectra. The association constants of d-amino acid methyl esters are found to be higher than those of their l-enantiomer. The sandwich-type binding of BaZn 2 L(ClO 4 ) 2 –DABCO supramolecular assembly was specially studied via 1 H NMR titration and 1 H ROESY. To understand the recognition on molecular level, density functional theory (DFT) calculations on B3LYP/LanL2DZ were performed on the minimal energy conformations of host, guests, and host–guest complexes. The minimal energy conformations were obtained by molecular mechanics (MM) optimization and molecular dynamics (MD) simulation. The results of single point energy, HOMO energy, and charges transfer were analyzed. The results of theoretical calculations are in good agreement with the experimental data.