Supramolecular self-assembly focuses on the studies of weak interactions beyond molecules and construction of complicated, well-defined supramolecular architectures which widely exist in natural process and have been used in catalysis, chemical sensing and molecular electronics. Utilization of tpy-MsupII/sup-tpy (M = metal) connectivity to construct specific shaped supramolecular architectures has been well-developed.Bisterpyridines possessing 60° and 120° directionality can readily form triangular and hexagonal metallomacrocycles with group 12 metals, such as: Zn(II) and Cd(II), respectively. The supramolecular rhomboidal architecture could also be formed through a multicomponent self-assembly utilizing a precise stoichiometric ratio (1:1:2) of bisterpyridines with 60° or 120° directionality and metal ions (Zn2+ or Cd2+). However, the triangular construct, which is formed solely by bisterpyridine with 60° branching angle, could also be detected in the same solution. To further probe the self-sorted formation of a rhomboidal architecture, a tristerpyridine possessing three adjacent terpyridine units is used. Such tristerpyridine ligand can readily react with 60°-directed bisterpyridine ligands and metal ions (Zn2+ or Cd2+) in the stoichiometric ratio (2:2:5) to quantitatively form a center-bridged, fused-triangular shaped, rhomboidal structure. A facile heteroleptic self-assembly of hexakisterpyridine and tristerpyridine possessing 60° angles between the adjacent terpyridine moieties with stoichiometric amount of Zn2+ ions (1:6:12) leads to the formation of supramolecular spoked wheel architecture in a 90% isolated yield, which is fully characterized by ESI-MS, NMR, and TEM imaging. When the central hexakisterpyridine of the spoked wheel is replaced with two staggered tristerpyridine ligands possessing 120° angle between the adjacent terpyridine units, a three-dimensional, supramolecular, bicycle-like wheel structure is readily formed, in which two 120°-directed tristerpyridines serve as the hub and spokes and six 60°-based tristerpyridines locate outside as rims. Another analogous supramolecular spoked wheel can also be formed by further redesign of the core ligand. Two tristerpyridine ligands possessing 60° between the adjacent terpyridine units adopt a parallel-staggered conformation with the opposite orientations to replace the core hexaligand. Eight equivalent amount of such tristerpyridine ligands (two serving as core ligands; six as outer rim ligands) can readily react with twelve equivalence of metal ions (Zn2+ or Cd2+) to form a supramolecular mandoline-shaped wheel structure, which contains two vertex-connected, centrally-bridged rhomboidal moieties at the concentration of > 15 mg·mL−1. When the concentration of the Cd2+-based mandoline-shaped structure is reduced, a quasi-tetrahedron structure possessing four tristerpyridine ligands and six Cd2+ ions can be detected and it becomes the only self-assembly product when the concentration is below 0.5 mg·mL−1. The Zn2+ analogue of the mandoline-shaped structure remains intact during the dilution and there is no quasi-tetrahedron structure detected in such supramolecular system.