Two macrocyclic dinuclear zinc(II) complexes (1a and 1b) have been self-assembled in the presence of pyridine and 2,2 -bipyridine, respectively, to form μ2-OH-bridged bimacrocycles with a Zn4O4 cavity through coordination bonding. The X-ray structural analysis reveals that both compounds {2a: [Zn4La 2(OH)2]2(ClO4)2; 2b: [Zn4Lb 2(OH)2]2(ClO4)2} have an open-mouthed sandwich-like structure with π−π interactions between parts of two phenyl rings to strengthen two hydroxyl groups connecting the metal atoms in the same direction of the macrocycle. Furthermore, nonclassical C−H•••Cl intermolecular interactions have been observed in the crystal of 2b. In addition, the reaction of 1a with quinoline derivatives has yielded novel hydrogen-bond-supported donor-acceptor complexes {3a: [Zn2 La(H2O)2(C10H9N)2](ClO4)2}. The crystallographic study of the complex containing 2-methylquinoline indicates that two 2-methylquinoline molecules are linked to two coordinating water molecules above and below the macrocyclic framework through O−H•••N hydrogen bonds. The 2-methylquinoline plane interacts in a face-to-face fashion with the phenyl ring of adjacent macrocyclic frameworks, forming an ordered arrangement where one macrocycle and two 2-methylquinolines are arrayed alternately with almost the same separation. The interplanar distance mentioned before is ca. 3.6Å.