Complexation ability of water-soluble calix[4]resorcinarene octacarboxylate toward phenol by the assistance of Fe(II) ions was investigated in aqueous solutions by photoluminescence (PL) and quantum-chemical methods. The results show that water-soluble calix[4]resorcinarene octacarboxylate forms stable sandwich-type complexes with phenols by 1:2 stoichiometry. The Fe(II) ions boost slightly the weak interaction between the pi-faces of the aromatic host and those of the guest predicted earlier in solvents which have high permittivity.