Complexation of chlorogenic acid (CA) by b-cyclodextrin (b-CD) at mildly acidic pH, was studied by fluorescence spectroscopy, isothermal titration calorimetry (ITC), cyclic voltammetry (CV) and NMR spectroscopy. Thermodynamic parameters (DH°, DS° and K) determined by both fluorescence and ITC, showed that the complexation of CA by b-CD is an enthalpy-driven process. Results show that CA molecule can be complexed through both polyphenolic and quinic acid moiety, leading to the formation of two supramolecular isomers with 1,1 stoichiometry.