Emulsions consisting of n-alkane/water using alpha, beta, and gamma-cyclodextrin (alpha, beta, and gamma-CD) as an emulsifier were prepared and characterized by means of several physicochemical techniques. A phase diagram of the n-alkane/CD/water system showed that an oil in water (O/W) emulsion can be prepared from a mixture of the appropriate composition. The dissolved n-alkane/CD complexes formed at low CD concentrations showed surface-activity, but emulsions could not be prepared from these complexes. On the other hand, the precipitated complexes formed at high CD concentrations when adsorbed to the oil/water interface, and served as an emulsifier for formation of emulsions. These results showed that the emulsions formed were of the Pickering emulsion. In addition emulsion formation was governed by the wettability and the surface free energy of the precipitated complexes.