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 extractants 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, K-chem), enthalpy of complex formation (Delta H), and stoichiometry (N) were directly measured with ITC, and the entropy of complexation (Delta S) was derived from these results. A first screening of K-chem toward phenol revealed a very high binding affinity for TOPO, and very low binding affinities for the other extractants. 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. K-chem 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 approximate to 3,5-dichlorophenol (in line with their pK(a) 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 extractant. The increase in binding affinity for TOPO in the phenol series was confirmed by a detailed ab initio study, in which Delta 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 Delta H value of -10.5 kcal/mol. In addition, these calculations confirm the formation of 1: 1 H-bonded complexes.