In this work the physicochemical behavior of a series of phytosterol ethoxylates in water is presented. The influence of the length of the polyoxyethylene chain is studied. The surfactant solutions have been examined by means of birifringent microscopy, surface tension, self diffusion 1H-NMR, dynamic and static light scattering, and rheology. The surfactants with a hydrophilic chain of 10 oxyethylene units or more gave a micellar region. The CMC values were generally very low and a reverse relationship between the CMC value and the polyoxyethylene chain length was obtained. The time required to reach equilibrium surface tension was very long, more then 150 minutes. For the hydrophobic surfactants large lamellar regions appeared while for the more hydrophilic surfactants cubic and hexagonal structures were present which remained stable up to temperatures of 100°C. In the micellar region prolate aggregates were formed which showed 'ghostlike' behavior, consisting of crossliked micelles with very fast relaxation times.