A phase diagram of a water-polyglyceryl didodecanoate ((C-11)(2)G(n)) system was constructed as a function of polyglycerol chain length (n) at 25degreesC. The average number of dodecanoic acid residues attached to polyglycerol is in the range of 1.6-2.3, and unlike commercial long-chain polyglycerol surfactants, unreacted polyglycerols were removed in the surfactants used. With an increase in the polyglycerol chain, the surfactant changes from lipophilic to hydrophilic, and the type of self-organized structure also changes from lamellar liquid crystals to the aqueous micellar solution phase via hexagonal liquid crystals. However, a discontinuous micellar cubic phase does not appear in the phase diagram, while it is formed in a long poly(oxyethylene)-chain nonionic surfactant system. In a dilute region, a cloud point is observed at a moderate polyglycerol chain length, napproximate to7. The cloud temperature is dramatically increased with a slight increase in hydrophilic chain because the dehydration of the hydrophilic chain length at high temperature is low compared with that of the poly(oxyethylene) chain. In other words, the phase behavior of (C-11)(2)G(n) is not very temperature sensitive. Three-phase microemulsion is formed in a water/(C-11)(2.3)G(7.3)/m-xylene system. The three-phase temperature or HLB temperature is highly dependent on the polyglycerol chain length.