Hybrids composed of nanoscale inorganic clusters and organic ligands are ideal models for understanding the different attractive forces during the self-assembly processes of complex macromolecules in solution. The counterion-mediated attraction induced by electrostatic interaction from the large, hydrophilic macroionic clusters can compete or cooperate with other types of attractive forces such as hydrophobic interactions, hydrogen bonding, pi-pi stacking, and cation-pi interactions from the organic ligands, consequently determining the solution behaviors of the hybrid molecules including their self-assembly process and the final supramolecular structures. The incorporation of organic ligands also leads to interesting responsive behaviors to external stimuli. Through the manipulation of the hybrid composition, architecture, topology, and solution conditions (e.g., solvent polarity, pH, and temperature), versatile self-assembled morphologies can be achieved, providing new scientific opportunities and potential applications.