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The terahertz attenuated total reflectance spectra of Poly(N-isopropylacrylamide) (P-NIPAAm) solutions were measured in the range of 26.5–47.3 °C. The phase-change in P-NIPAAm was observed via the temperature dependence of the spectra. The collapse of hydrogen bonds in solution was confirmed by the decrease in the signal intensities around 62 cm-1, which corresponds to fast dielectric relaxation by rotation and collision of molecules, and around 166 cm-1, which corresponds to the stretching mode of the intermolecular vibration of water molecules.