In this study, the phenyl sulfonic acid (PhSA) modified carbon nanotubes (CNTs) were used for benzene removal from waters by  (D- μSPE). Due to adsorption mechanism, π–π interactions was provided between the aromatic ring of benzene with the surface (SO3H) and phenyl ring (-C6H5) of CNTs, respectively. Therefore, 20-100 mg of sorbent, concentration of benzene (0.1–10 mg L-1), pH (1-12) and contact time (5–120 min) were investigated and optimized for benzene removal from water samples in static system. The concentration of benzene in water was determined by (SHS-GC-MS). The results showed, the Langmuir-Freundlich (LF) isotherm provided the best fit for benzene sorption. By using the Langmuir model, the maximum adsorption capacity of 117.34 and 22.86 mg/g was achieved for benzene removal from waters with CNTs@PhSA and CNTs, respectively. Under optimal conditions, adsorption efficiency of CNTs@PhSA and CNTs was obtained 97.7% and 20.6 % for benzene removal from water samples, respectively.