Vermiculite is widely used in the field of wastewater treatment due to its good adsorption and ion exchange properties. A large number of hydrophilic inorganic cations are filled between the layers of natural vermiculite, which produce a thin water film on the mineral surface and reduce its organic wastewater adsorption capacity. To improve the adsorption ability of vermiculite for naphthalene sulfonic acid, natural vermiculite was pretreated using acid activation, and then modified by trioctylamine (TOA) to prepare TOA modified acid-activated vermiculite (TOA-Hts), which possessed the vermiculite with adsorption and extraction properties. The prepared samples were characterized by XRD, FT-IR and BET methods. The influence of solution pH value and TOA-Hts dosage on the adsorption performance was studied, and the adsorption mechanism of TOA-Hts was analyzed. The results show that, the R′SO-3 ions in wastewater are majority adsorbed on TOA-Hts by complex extraction reaction with TOA. Compared with natural vermiculite, the naphthalene sulfonic acid removal rate of TOA-Hts is increased by 90.63%, and the adsorption quantity reaches 78.98 mg·g-1. The adsorption process can be described by the Freundlich model and pseudo-second-order kinetics model.