Water is one of the most important and basic materials in living systems which has been extensively studied because of its peculiar properties and abnormal properties. Raman spectral study on the water molecular structure is highly desirable. It obtains the information of molecular vibration and rotation to understand the structure and the interaction of water molecules. The Raman spectra of ice Ih surface of film is obtained in the temperature range of -20 to -190 ℃ at atmospheric pressure. The spectra show that O∶H van der Waals bond and O—H polar-covalent bond shift to higher and lower wave number, respectively. The relationship between Raman shift and temperature is linear, by comparing the slope of different vibration modes to determine the relationship between the expansion and contraction of the bond length, which reveal that the ice Ih density increases with cooling. The results indicate that it is important for hydrogen bond in the process of cooling. Meanwhile, Raman intensity of O—H bond vibration mode and O∶H bond vibration mode occur a mutation at -150 ℃, this results showed that the phase transition of ice Ih-ice Ⅺ (i. e. proton-ordered phase of ice Ih).