Na2O(K2O)—CaO(MgO)—SiO2, Na2O(K2O)—Al2O3—SiO2, Na2O(K2O)—B2O3—SiO2, Na2O(K2O)—PbO—SiO2 and PbO—BaO—SiO2 glass systems were investigated using laser Raman spectroscopic technique. The modification of short-range structure of glass caused by network modifier cations will influence Raman signature. Alkali and alkali-earth ions can weaken the bridging oxygen bond, thus lower the frequency of Si—Ob—Si anti-symmetric stretching vibration. When coordinated by oxygen ions, B3+ can form ［BO4］ tetrahedron and enter the silicon-oxygen network, but this effect had little impact on the frequency of Raman peaks located in the high-frequency region. Al3+ can also be coordinated by oxygen ions to form ［AlO4］ tetrahedron. ［AlO4］ will increase the disorder degree of network while entering network. Ba2+ can increase the density of electron cloud along the Si—Onb bond when it bonds with non-bridging oxygen, which will lead to a higher peak intensity of O—Si—O stretching vibration. The Raman peaks of alkli- and alkali-earth silicate glasses are mainly distributed in the region of 400~1 200 cm-1, while in the spectrum of Na2O(K2O)—PbO—SiO2 glass system a 131 cm-1 peak existed. The authors assigned it to the Pb—O symmetric stretching vibration. Some of the samples were produced in the laboratory according to the average compositions of ancient glasses, so this research is very significant to discriminating ancient silicate glasses of different systems by Laser Raman spectroscopic technique.