Tripodal amphiphilic molecules toward organic-inorganic hybrid emulsions were successfully synthesized based on incompletely condensed polyhedral oligomeric silsesquioxanes (POSSs). The three silanol groups provide an excellent scaffold for the construction of three-dimensional amphiphilic molecules, thus well-defined tripodal amphiphilic POSS derivatives were readily synthesized. Thermal analyses revealed that an incompletely condensed POSS exhibited lower crystallinity without loss of thermal stability in comparison with a completely condensed POSS, whereas readily forms aggregates because of its high crystallinity. The newly synthesized tripodal amphiphilic POSSs possessed good solubility in water and effectively stabilized oil-in-water emulsions, while a conventional mono-substituted amphiphilic POSS did not work as an emulsifier because of its lack of water solubility. The prepared organic-inorganic hybrid emulsions were stable against coalescence, and no demulsification occurred over 1 month.