Ambient temperature Raman spectra of four typical chain silicate mineral crystals were determined and the vibrational modes have also been simulated through Cambridge Serial Total Energy Package(CASTEP) function based on density functional theory (DFT). Analysis of the various vibrational modes combined with SIT (stress index of tetrahedron), which expresses the characteristics of the microstructure of alumina silicates.The results show that the CASTEP calculation is an effective and practical calculation method to simulate Raman spectra of the aluminasilicates, and help to assign the vibrational modes. The concept of SIT also has its application on studying the correlation between Si-Onb symmetric stretching vibration and the minerals local environment of SiOT.