In this work, we investigated the anodic stability and decomposition mechanism of sulfolane (SL). The anodic stability of SL-based electrolyte with different lithium salts on Pt and LiNi0.5Mn1.5O4 electrodes was found to decrease as follows: LiPF6/SL>LiBF4/SL>LiClO4/SL. The oxidation potential of 1M LiPF6/SL electrolyte on both Pt and electrodes is about 5.0V vs Li/Li+. The presence of PF6 - and another SL solvent dramatically alters the decomposition mechanism of SL. Oxidation decomposition of SL-SL cluster is the most favorable reaction in LiPF6/SL electrolyte. The dimer products with S-O-R group were detected by IR spectra on the charged LiNi0.5Mn1.5O4 electrode surface and in the electrolyte near the electrode surface, and were found to increase the interfacial reaction resistance of the LiNi0.5Mn1.5O4 electrode.