Viscoelastic solutions formed in a catanionic surfactant system of dodecyltriethylammonium bromide (DTEAB)/sodium dodecylsulfate (SDS) at the molar ratio of 27/73 were systematically studied using a combination of rheology and dynamic light scattering (DLS). Wormlike micelles began to form above the total surfactant concentration (C-total) of 120 mM by the growth of small cylindrical micelles. Subsequently the system Was found to exhibit linear viscoelasticity with characteristic of a Maxwell fluid in the intermediate concentration range of 170-210 mM, which arose from a 3D entangled network of wormlike micelles. At higher surfactant concentrations, a transition from linear micelles to branched structures probably took place. Finally and significantly, the effect of the surfactant headgroup on the theological property of catanionic surfactant mixtures was discussed. (C) 2009 Elsevier Inc. All rights reserved.