The phase behavior, rheological properties, and structures of two salt-free catanionic surfactant systems, tetradecyltrimethylammonium hydroxide ((ITA)OH)/lauric acid (LA)/H2O and cetyltrimethylammonium hydroxide ((CTA)OH)/LA/H2O, in the presence of deoxycholic acid (DeCA) were investigated and compared with the results of cholic acid (CA). Small-angle X-ray scattering, deuterium nuclear magnetic resonance, and rheological measurements were employed to monitor the phase structure and transition. The surface tension was used to investigate the surface activities of the bile acid/(TTA)OH and bile acid/(TA)OH mixtures in dilute solutions. The results show that they have a minimum surface tension in a solution with excess cationic surfactant, and the critical micelle concentration decreases with an increase of the cationic surfactant chain length and hydrophobicity of the bile acids. At equimolar mixtures of DeCA and cationic surfactants, or DeCA being in excess, phase separation occurs with a large diameter of droplets in the upper phase and a small volume of viscous liquid in the bottom phase. Compared with CA systems, in the salt-free catanionic surfactant systems containing DeCA, phase transition from the birefringent L-alpha phase to the L-1 phase occurs at a high molar fraction of DeCA, and the viscosity is higher at the same molar fraction of bile acid, indicating the significant influence of the molecule structures of bile acids despite only one hydroxyl group difference. Shear thickening is observed in the L-alpha region, and a gradual evolvement of aggregates is predicted. Longer chain cationic surfactant can also increase the shear viscosity, which could be ascribed to the increase of the critical packing parameter, but with less influence on the phase transition.