To investigate the adsorption properties and mechanisms of haloacetonitriles (HANs), large-pore SBA-15 mesoporous silica (SBA-CHX) was synthesized using cyclohexane as a swelling agent, and the surface was modified with polymerizable gemini surfactant (PG). The structure and textural properties of the synthesized adsorbents were characterized. PG surfactant coverage on the surface and the degree of polymerization were confirmed with FT-IR analysis. Adsorption experiments were performed under batch conditions to evaluate the influence of the contact time, adsorption isotherms, the effect of the pH solution, and the selective adsorption of five haloacetonitriles (HAN(5)) in individual-solute and mixed-solute solutions and surfactant leaching studies. The results indicated that the hydrophobic HANs were efficiently adsorbed onto PG surfactant-modified SBA-CHX. The selective adsorption mechanisms involved a more complex interplay between the organic partition, surface adsorption (i.e., ion-dipole electrostatic interactions) and hydrophobic interaction that depended upon the adsorbent and adsorbate characteristics. An increased degree of halogen substitution in the HAN molecule significantly affected the adsorption capacity and selectivity by the organic partition. Polymerization of the polymerizable surfactant increased the stability of the adsorbed surfactant on the adsorbent surface. (C) 2012 Elsevier B.V. All rights reserved.