Conventional cationic and anionic (catanionic) surfactant mixtures tend to form precipitates at the mixing molar ratio of the cationic and anionic surfactant of 1:1 because of the excess salt formed by their counterions. By using OH- and H+ as the counterions, however, excess salt can be eliminated, and salt-free catanionic systems can be obtained. Here, we report the detailed phase behavior and rheological properties of salt-free catanionic surfactant system of tetradecyltrimethylammonium hydroxide (TTAOH)/lauric acid (LA)/H2O. With the variation of mixing molar ratio of LA to TTAOH (rho=nLA/nTTAOH), the system exhibits much richer phase behavior induced by growth and transition of aggregates. Correspondingly, the rheological property of the system changes significantly. Take the series of samples with fixed total surfactant concentration (cT) to be 15 mg.mL(-1), the system only forms a low viscous L 1 phase with a Newton fluid character at the TTAOH-rich side. With increasing rho, first a shear-thickening L1 phase region is observed at 0.70<or=rho<or=0.80, and then the system reaches a viscoelastic L1 phase region at 0.80<rho<0.88, which exhibits Maxwell fluid character. With further increasing rho, an L1/L alpha two-phase region reaches with birefringent L alpha phase at the top, and after that a bluish vesicle phase is observed at 0.92<rho<1.05. At the LA-rich side, phase separation of the bluish vesicle phase occurs at rho>or=1.05, and finally, at rho>or=1.13, the excess LA will separate from the bulk solution and form a white top layer. Investigations were also carried out by varying c T at fixed rho and by changing temperature, respectively. It was found micelle growth would be greatly suppressed at higher temperatures. However, the vesicle phases showed a considerable resistance against temperature rise.