Thermodynamic study on the interaction of β-CD with poly ethylene oxide and poly acrylic acid was performed by isothermal titration calorimetry at 298K. when β-CD is added to the interpolymer complex, competition is created between host-guest and Hydrogen bond. Enthalpy of interaction between the β-CD and interpolymer complex was calculated using the extended solvation theory. P=1 Shows that willingness of β-CD to interact with both polymers is identical. The positive values of and show that interpolymer complex are stabilized by β-CD . The process is both enthalpy and entropy-driven. The results show that this interaction is exothermic and increases the interpolymer complex stability.