In this work, the effect of octane concentration on the phase behavior of CTAB/water/l-butanol system was studied by using pulsed field gradient spin-echo NMR measurements and freeze fracture electron microscopy (Cryo-TEM and FFEM). When the octane concentration increases, the liquid crystalline phase is destabilized and a continuous single-phase microemulsion region from the water apex to the oil apex is formed. The conductivity behavior has a distinct percolative phenomenon, which indicates that the single-phase microemulsion is changed continuously from oilin-water (o/w) structure via a bicontinuous structure to water-in-oil (w/o) structure. This result is consistent with those of the PGSE-NMR, Cryo-TEM, and FFEM. In the w/o region, the self-diffusion coefficient of water is relatively high «1---6) X 10-l0 m • S-l) due to the higher solubility of water in the continuous phase consisting of octane (10% by weight) and I-butanol. The penetration of a large amount of octane molecules between surfactant chains results in the much lower self-diffusion coefficient of octane.Microemulsions are transparent, isotropic, thermodynamically stable dispersions of oil and water, stabilized by surfactant molecules [l]. Four-component systems of surfactant, cosurfactant (generally a short chain linear alcohol), oil, and water have many important features and are the most intensively studied microemulsion systems. The reason for the significance of these systems is that the introduction of cosurfactant greatly extends the isotropic solution region, especially with single chain ionic surfactants. One of the most basic aspects of any surfactant system, besides thermodynamic stability, is its microstructure. Microemulsions based on cationic surfactant cetyltrimethylammonium bromide (CTAB) have been extensively used as hosts for enzymes and microreactor for polymerization and preparation of nanosize particles. Despite such widespread interest in CTAB microemulsion, the structure of a quaternary microemulsion is not easy to verify, which can be seen from the fact that several studies, 1272 despite the use of a wide range of experimental techniques, have made only a little progress in getting a reliable picture of these systems. A useful characterization of microemulsions is via the identification of whether the oil and water domains are closed (to form "droplets") or not; hence a classification into oil-in-water (o/w) droplets, w/o droplets, and "bicontinuous" structures [2]. A well-established method for detecting changes of the microstructure of microemulsions is the measurement of self-diffusion coefficients by NMR techniques. On the time scale of NMR experiments one is concerned with molecular self-diffusion over macroscopic distances of the order of micrometers (i.e. distances much larger than the size of microemulsion droplets). Therefore, the experiment is not sensitive to molecular displacements within the droplets. Accordingly, in the case of an o/w microemulsion the monitored translation of the oil molecules in the droplet ...