The surface and mixed micellization properties of the aqueous binary mixed system of alkanediyl-α, ω-type cationic gemini surfactant, 14–4–14 and conventional nonionic surfactant, Brij-58 in an aqueous medium have been investigated over the entire mole fractions at 298.15K. The critical micelle concentration (cmc) for each mixture have been measured by tensiometric and fluorescence measurements. The solution and adsorption characteristics like composition, activity coefficients and mutual interaction parameters have been computed using different proposed theoretical models like Clint, Rosen, Rubingh, Motomura and Maeda. The strength of interaction of the surfactant is attributed to the sterical and electrical factors on mixed monolayer and micelle formation and of surfactant–surfactant interactions. The micellar aggregation number (Nagg) has also been measured using steady state fluorescence quenching method at a total concentration of ~1mM of pure components as well as their mixtures of different ratios. The micropolarity and binding constant were determined from the ratio of intensity (I1/I3) of peaks of pyrene fluorescence emission spectrum.