Supramolecular self-assembly refers to the spontaneous formation of highly ordered complex structures through non-covalent interactions such as hydrogen bonding, π-π stacking, host-guest interactions, hydrophobic/hydrophilic interactions, and so on. The self-assembly process can give rise to different supramolecular structures, including supramolecular macrocycles, cages, frameworks, et al. The determinants of the formation of various self-assembled structures are influenced by various factors, including molecular design, the driving forces (diversified non-covalent interactions), solvent effects, external conditions (concentration, temperature, pH, et al.), and so on. Among all the self-assembly processes, the study of aqueous self-assembly holds significant importance due to its relevance to biology and potential biomedical applications. Many biological processes, such as protein folding, enzyme activity, and cell signaling, occur in aqueous environments. By studying aqueous self-assembly, we can gain insights into the fundamental principles underlying biological self-assembly and mimic biological processes for biomedical applications. However, the study of self-assembly in water presents several challenges due to the unique characteristics of the aqueous environment. For example, micelles and vesicles can be readily induced by conventional amphiphiles bearing a hydrophilic head and hydrophobic tail in aqueous media. However, achieving precise control over these self-assembly structures proves challenging due to the inherently random self-assembly process in water. Nature's well-defined cavities or channels often assume a central role in biochemical processes. The establishment of meticulously self-assembled nanostructures in aqueous environments holds significant promise within the realms of biology and medicine. Controlling the hydrophobicity/hydrophilicity properties and interactions of molecules is crucial for constructing supramolecular structures with specific functions. Herein, we intend to introduce both hydrophilic and hydrophobic moieties into a molecular structure simultaneously. By tuning the linkages between hydrophilic and hydrophobic parts, the self-assembly behaviors and structural morphologies can be controlled. Two structurally similar precursors containing hydrophobic hexaphenylbenzene core and hexa-substituted hydrophilic methylpyridine as edges were designed and synthesized. The only difference in the structures of these two precursors is the flexible double bond or the rigid single bond as bridges (Figure ). Two completely different self-assembly structures were observed in water under the same conditions. Compound M1-X (X = I -or Cl -) was self-assembled into a two-dimensional framework with well-defined channels, while a supramolecular cage was obtained through the self-assembly of M2-I. The single-crystal X-ray diffraction (SCXRD) provided unequivocal evidence of the 2D framework from M1-X (X = I - or Cl -) and the cube-like structure assembled from M2-I. These diversified self-assemblies in water open up new possibilities for designing and synthesizing advanced materials and nanoscale structures. By subtle tailoring of the molecular structure and controlling the interactions between different components, a diverse array of materials with unique properties can be constructed.