Mixed surfactant solutions are studied to understand their synergistic effects. Here we report the micellization properties of mixed surfactant solutions of the gemini surfactant N,N'-bis(dimethyldodecyl)-1,2-ethanediammoniumdibromide (12-2-12) with the imidazolium ionic liquid 1-dodecyl-3-methylimidazolium bromide (C(12)mimBr) investigated by isothermal titration calorimetry (ITC), conductometry, fluorimetry, and dynamic light scattering (DLS). A two-parameter Margules model was successfully used to correlate the cmc values and calculate the compositions and activity coefficients of the two components in the mixed micelle phase for 12-2-12/C(12)mimBr aqueous solutions with different overall surfactant compositions. The dissociation degree of counterion, the thermodynamic quantities of micellization, and the excess thermodynamic quantities for the mixed micelle were calculated and discussed. The ITC experiment in the low overall surfactant composition region showed a second phase transition. A thermodynamic model was proposed to explore phase behaviors of two different types of micelle and their solution, which was further confirmed by fluorescence and DLS studies.