The characteristics of sodium 4-decyl naphthalene sulfonate (SDNS)/Triton X-100 (TX-100) and sodium dodecyl sulfonate (SDSN)/SDNS mixed micelles with different molar ratios were studied by 1D and 2D 1H NMR. In the mixed micelle of SDNS/TX-100 the phenoxy rings of the TX-100 are embedded in the near vicinity of the alkyl chains of SDNS and its polyoxyethylene segments, but the first oxyethylene group, to which the phenoxy ring is adjacent, are located near the naphthyl rings. In the mixed micelle of the SDNS/SDSN system the sulfonate groups of SDSN are embedded in the naphthyl rings of SDNS; i.e., they are located more internally in the mixed hydrophobic micellar core than those of SDNS. Moreover, the naphthyl rings of SDNS separating these sulfonate groups of SDSN may play an active role in weakening the electrostatic repulsion of the negatively charged sulfonate groups, which favors the mixed micelle aggregation.