The corrosion behaviors of perovskite La0.8Sr0.2Co0.3Fe0.7O3−δ (LSCF) in the sodium tetrasulfide melt have been studied to demonstrate its possibility to be used as a coating material for the positive current collector in the sodium sulfur battery (Na/S). The electrochemical techniques including potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) are applied in the study. The results demonstrate that the corrosion process of the LSCF in sodium tetrasulfide melt is activation controlled. The corrosion current density of the LSCF is approximate 10 times smaller than that of the 316L stainless steel. Two compact corrosion layers which may act as a stable barrier retarding the corrosion process have formed on the surface of LSCF after immersed for 130 days. The promising results suggest that LSCF exhibits high corrosion resistance against molten sodium tetrasulfide and may be an appropriate candidate coating material for the positive current collector in Na/S battery.