Surface tension and aggregation behavior in an aqueous solution of the mixture of cationic surfactant oleyl bis(2-hydroxyethyl)methylammonium bromide (OHAB) and anionic surfactant sodium dodecyl sulfate (SDS) have been studied by surface tension, conductivity, turbidity, zeta potential, isothermal titration microcalorimetry (ITC), cryogenic transmission electron microscopy (Cryo-TEM), and dynamic light scattering. The mixture shows pretty low critical micellar concentration and surface tension, and successively forms globular micelles, unilamellar vesicles, multilamellar vesicles, rod-like micelles, and globular micelles again by increasing the molar fraction of OHAB from 0 to 1.00. The cooperation of hydrophobic interaction between the alkyl chains, electrostatic attraction between the headgroups as well as hydrogen bonds between the hydroxyethyl groups leads to the abundant aggregation behaviors. Furthermore, the solubilization of zein by the OHAB/SDS aggregates and their interactions were studied by ITC, total organic carbon analysis (TOC), and Cryo-TEM. Compared with pure OHAB or pure SDS solution, the amount of zein solubilized by the OHAB/SDS mixture is significantly reduced. It means that the mixtures have much stronger abilities in solubilizing zein. This result has also been proved by the observed enthalpy changes for the interaction of OHAB/SDS mixture with zein. Mixing oppositely charged OHAB and SDS reduces the net charge of mixed aggregates, and thus, the electrostatic attraction between the aggregates and zein is weakened. Meanwhile, the large size of the aggregates may increase the steric repulsion to the zein backbone. This work reveals that surfactant mixtures with larger aggregates and smaller CMCs solubilize less zein, suggesting how to construct a highly efficient and nonirritant surfactant system for practical use.