A hybrid organic–inorganic material based on vermiculite was prepared to remove diethyl phthalate (DEP) from aqueous solution. Natural vermiculite was activated with HCl to improve the specific surface area and was then modified by silanization using trimethylchlorosilane. Organovermiculite prepared by ion exchange with hexadecyl trimethylammonium bromide (HDTMAB) was also tested for comparison. The leaching of 2molL−1 HCl at 80°C increased the specific surface area of vermiculite from 14.4 to 500.0m2g−1, and the average pore-diameter was decreased from 7.90nm to 2.75nm. Fourier transform infrared spectroscopy (FTIR) spectra indicated that trimethysilyl groups were grafted covalently on the surface of acid vermiculites. The specific surface area of trimethylchlorosilane-modified acid vermiculites (TMAVs) (355.4m2g−1) was much larger than that of organovermiculite (6.0m2g−1). The isotherm adsorption experiments of DEP showed that TMAVs exhibited linear isotherms, suggesting that the uptake of DEP was controlled by partitioning mechanism. The maximal partition coefficient (Kd) of TMAVs was 3.1 times higher than that of organovermiculite, implying that TMAVs had stronger organic affinity than organovermiculite. The results demonstrate that the adsorption capacity and mechanism of organoclays were controlled by the specific surface area and organic loading, whereas the length of alkyl chain of organic modifier was not the key factor.