Benzene, toluene, ethylbenzene, and xylene are frequently observed contaminants in industrial wastewaters causing concerns about environmental and health effects. An aqueous surfactant two-phase (ASTP) extraction system using mixtures of cationic and anionic surfactants have been shown to be a promising surfactant-based separation technique to concentrate solutes such as proteins and dyes from aqueous solution. A phase separation of a surfactant solution occurs at certain surfactant compositions and concentrations, forming two isotropic phases. One is rich in surfactant aggregates (surfactant-rich phase) and the other is lean in surfactant aggregates (surfactant-dilute phase). Most of the organic contaminants tend to solubilize and concentrate in the surfactant-rich phase, leaving the surfactant-dilute phase containing only small amounts of contaminants as remediated water. The effect of NaCl addition on the critical micelle concentration (CMC) and the extraction ability of ASTP formed by mixtures of cationic surfactant (dodecyltrimethylammonium bromide; DTAB) and anionic surfactant (alkyl diphenyloxide disulfonate; DPDS) at 50 mM total surfactant concentration with a 2:1 molar ratio of DTAB: DPDS was investigated; the CMC of the mixture slightly decreases with increasing NaCl concentration. The extraction and preconcentration of benzene are greatly enhanced by added NaCl. The higher the degree of hydrophobicity of contaminants, the greater the extraction into the surfactant-rich phases. At 1.0 M NaCl addition, about 95% of xylene, 92% of ethylbenzene, 90% of toluene, and 79% of benzene are extracted into the surfactant-rich phase within a single stage extraction and the contaminant partition ratios can be as high as 395 for xylene, 273 for ethylbenzene, 206 for toluene, and 84 for benzene, which are greater than those obtained from the conventional ASTP extraction system using nonionic surfactants.