In this work, the formation of supramolecular mixed micelles from a hexamethylated p-sulfonatocalix[6]-arene (SC6HM) derivative and a conventional cationic surfactant (dodecyltrimethylammonium bromide, C(12)TAB) was investigated by surface tension and using pyrene as a micropolarity fluorescent probe to gain insights into the role of the calixarene concentration on the aggregation behavior. The formation of micelles at a concentration well below the critical micelle concentration of pure surfactant was observed in the presence of very low concentrations of SC6HM (below the micromolar range). Interestingly, the critical micelle concentration of the mixed system was shown to be rather insensitive to the concentration of SC6HM. On the other hand, the concentration of mixed micellar aggregates was demonstrated to be highly dependent on the macrocycle concentration and less dependent on the C(12)TAB concentration in the range between the critical micelle concentrations of the mixed systems and pure surfactant.