The lower critical solution temperature (LCST) phase separation behaviors of thermosensitive poly(N-isopropylacrylamide) (PNIPAM) aqueous solutions were investigated by power-compensation differential scanning calorimetry (DSC). The entropic effect and hence the change of swelling state of PNIPAM polymer coils in homogeneous concentrated aqueous solutions with varied solution composition was elucidated by the isothermal enthalpy demixing recovery behaviors in distinct concentration regions.