Thin films of SrBi2Nb2O9 (SBN) with thickness of 0.1, 0.2, 0.3 and 0.4 μm were grown by sol-gel technique on platinum/silicon substrates, and annealed at 800°C. Raman spectra of the samples present bands around 170,210, 272, 300,430, 580, 717, and 839 cm−1 which correspond to the SBN formation. The prominent Raman band around 839 cm−1, which is the Alg mode of the orthorhombic symmetry, is assigned to the symmetric stretching of the NbO6 octahedrals. The frequency of this band is found to shift at different places in the same sample, as well as from sample to sample. The frequency and width variations of the Raman bands are discussed in term of ions in non-equilibrium positions, which seem to be related with the crystallization degree in the SBN samples. Also, the Raman study indicates the presence of foreign sharp peaks, which are associated with the coexistence of phases other than SBN. The thickness dependence of the Raman spectra and the X-ray diffraction are also discussed. Finally, the experimental results of the SBN/Pt/Si films grown at 800°C are compared with those obtained at 650°C.