A series of cationized hydroxycelluloses (cat-HEC) with different molar substitution have been synthesized. The forming interactions between sodium dodecyl sulfate (SDS) with cat-HEC and their temperature-dependent rheological behavior have been studied by steady-shear rheometry. Different molar substitution and the concentration of SDS can effect the rheological behavior of polymer matrices. Self-assembly behaviors of these supramolecules in water were studied through transmission electron microscopy (TEM). The results showed that different shapes were observed if increasing molar of SDS.