Amphiphiles of inorganic-organic hybrids, which consist of hydrophilic inorganic heads and hydrophobic organic tails, have unique solution behaviors of self-assembling into various structures like micelles and vesicles. The self-assembly/disassembly is triggered by different kinds of stimuli like light, heat, magnetic field and solvent polarity. Moreover, the morphology and size of the assemblies are usually tunable by experimental conditions and molecular structures. The driving forces for the self-assembly behavior are the combination of electrostatic interaction, hydrophobic interaction, hydrogen bonding, it-1t stacking, etc. Normally, only one of the driving forces is dominant, depending both on the molecular structures and external stimuli. Therefore, the inorganic-organic hybrids with rationally controlled self-assembly behaviors and adjustable functionality are ideal materials for sensors, heterogeneous catalysts, biomaterials and so on.