Raman scattering spectra are used to investigate LiF cluster‐based nanophase films. The experiments confirm the existence of multi‐order‐like Raman scattering and surface phonon modes. Good agreement is achieved between the observed spectral lines and the calculated results if the Raman scattering lines are attributed to an appropriate linear combination of primary modes and surface optical modes. The fine structure observed in the case of the smaller cluster has reflected the intensity of the cluster‐substrate interaction, which may result in the splitting of Raman peaks. ©1995 American Institute of Physics.