A porous sludge-derived char was prepared by a new one-step pyrolytic process with citric acid-ZnCl2 mixed fabricating-pore agents. The sludge-derived char was confirmed to be a hierarchically porous hybrid adsorbent containing-elemental carbon, -highly carbonized organic species and -inorganic ash with a great surface area of 792.4 m(2) g(-1). It was used as a carbon-based hybrid adsorbent for four benzene derivatives including 4-chlorophenol, phenol, benzoic acid and 4-hydroxylbenzoic acid in aqueous solution. Results showed that their sorption isotherms were nonlinear at low concentrations and linear at high concentrations. The sorption performance could be described by a multiple sorption model (Q(T) = Q(A) + KPCe). The order of these partition sorption coefficients (K-P) of these benzene derivatives was consistent with their octanol-water partition coefficients (logK(ow)), but those saturated amounts (Q(A)) were inconsistent with their logK(ow). The inconstancy was found to be considerably dependent on the preferential interaction of benzoic acid with SiO2 in the sludge-derived char. Quantum theoretical calculation confirmed that the preferential interaction was attributed to the formation of hydrogen bonds (1.61 and 1.69 angstrom) and new Si-O bonds (1.83 and 1.87 angstrom) between the carboxyl of benzoic acid and the SiO2 surface in the sorption process. (C) 2014 Elsevier B.V. All rights reserved.