To develop a new solvent-impregnated resin system for the removal of phenols from water the complex formation of triisobutylphosphine sulfide (TIBPS), tributylphosphate (TBP), and tri-n-octylphosphine oxide (TOPO) with a series of phenols (phenol, thiophenol, 3-chlorophenol, 3,5-dichlorophenol, 4-cyanophenol, and pentachlorophenol) was studied. The investigation of complex formation between the extradants and the phenols in the solvent toluene was carried out using liquid-liquid extraction, isothermal titration calorimetry (ITC), and quantum chemical modeling (B3LYP/6-311+G(d,p)//B3LYP/6-311G(d,p) and MP2/6-311++G(2d,2p)//B3LYP/6-311G(d,p)). The equilibrium constant (binding affinity, Kchem), enthalpy of complex formation (¿H), and stoichiometry (N) were directly measured with ITC, and the entropy of complexation (¿S) was derived from these results. A first screening of Kchem toward phenol revealed a very high binding affinity for TOPO, and very low binding affinities for the other extradants. Modeling results showed that although 1:1 complexes were formed, the TIBPS and TBP do not form strong hydrogen bonds. Therefore, in the remainder of the research only TOPO was considered. Kchem of TOPO for the phenols in toluene increased from 1 000 to 10 000 M-1 in the order phenol <pentachlorophenol <3-chlorophenol <4-cyanophenol ˜ 3,5-dichlorophenol (in line with their pKa values, except for pentachlorophenol) in the absence of water, while the stoichiometric ratio remained 1:1. In water-saturated toluene, the binding affinities are lower due to co-complexation of water with the active site of the extradant. The increase in binding affinity for TOPO in the phenol series was confirmed by a detailed ab initio study, in which ¿H was calculated to range from -10.7 kcal/mol for phenol to -13.4 kcal/mol for 4-cyanophenol. Pentachlorophenol was found to behave quite differently, showing a AH value of -10.5 kcal/mol. In addition, these calculations confirm the formation of 1:1 H-bonded complexes. © 2008 American Chemical Society.