The structure of Na2Si2O5 from room temperature up to 1,773 K are studied by high temperature Raman spectroscopy using copper vapor pulse laser and integral time-resolved detection technique without any black-body radiation effect on spectral record. Back-scattering optical configuration is coupled with confocal collection of Raman signal of macro-sample in the high temperature shaft tube furnace. Results show that temperature-dependent Raman spectra can clearly indicate phase transition during melting. Relative densities of various kinds of SiO4(n-4) (n, bridging-oxygen number binding to one tetrahedron former Si) tetrahedrons can be qualitatively and quantitatively resolved by Gaussian spectral deconvolution. Obviously high temperature Raman spectroscopy provides an useful tool for the micro-structure research of materials under high temperature.