The interfacial and micellization behavior of three dicarboxylic amino acid-based anionic surfactants, abbreviated as AAS (N-dodecyl derivative of -aminomalonate, -aspartate, and -glutamate) in combination with hexadecyltrimethylammonium bromide (HTAB) were investigated by surface tension, conductance, UV−vis absorption/emission spectroscopy, dynamic light scattering (DLS), and viscosity studies. Critical micelle concentration (CMC) values of the surfactant mixtures are significantly lower than the predicted values, indicating associative interaction between the components. Surface excess, limiting molecular area, surface pressure at the CMC, and Gibbs free energy indicate spontaneity of the micellization processes compared to the pure components. CMC values were also determined from the sigmoidal variation in the plot of micellar polarity and pyrene UV−vis absorption/ emission intensities with surfactant concentration. The aggregation number, determined by static fluorescence quenching method, increases with decreasing mole fraction of the AAS (α AAS ), where the micelles are mainly dominated by the HTAB molecules. The size of the micelle increases with decreasing α AAS , leading to the formation of larger and complex aggregates, as also supported by the viscosity studies. Micelles comprising 20−40 mol % AAS are highly viscous, in consonance with their sizes. Some of the mixed surfactant systems show unusual viscosity (shear thickening and increased viscosity with increasing temperature). Such mixed surfactant systems are considered to have potential in gel-based drug delivery and nanoparticle synthesis.