A gradient pyrolysis approach has been adopted for synthesis of ordered mesoporous carbonaceous materials with different surface and textural properties for removal of hexachlorobenzene. The resultant ordered mesoporous carbonaceous materials possess high surface areas (364-888 m2/g), large pore volumes (0.23-0.47 cm3/g), uniform pore sizes (2.6-3.8 nm), and tunable hydrophobic properties. They show high-efficiency removal performances for hexachlorobenzene with high adsorption capacity of 594.2-992.1 μg/g. An enhanced removal rate (>99%) can be obtained with the increasing pyrolysis temperature (900 °C) as a result of the strong hydrophobic-hydrophobic interaction between the carbon framework and hexachlorobenzene molecules. Furthermore, the adsorption behaviors follow the Sips isotherm model and obey the pseudo-first-order kinetic model.