Raman spectra of Li2B4O7 at different temperatures up to 1 373 K were recorded by using in situ high temperature Raman spectroscopic technique. With the increase of temperature, Raman spectra of crystal broaden and decrease in wavenumber and intensity. During the melting process, ［B4O9］ rings which consist of two ［BO4］ and two ［BO3］ turned into (B3O6)3- six-membered ring and ［BO3］, ［BO4］ species decreased and then disappeared. In addition, the vibrational modes of the Li2B4O7 crystal were simulated and assigned by using density functional theory(DFT)method. Raman spectra of x(Li2B4O7)(x=2, 3, …, 9) rings which consist of (B3O6-BO3) were calculated by using quantum chemistry ab initio method, to analyze the cluster in melt. It can be concluded that there exists super ring structure which contains three (B3O6-BO3) rings connected with each other.