: The over-discharging phenomena in sodium-nickel chloride batteries were investigated in relation to decomposition of molten salt electrolyte and consequent metal co-deposition. From XRD analysis, the material deposited on graphite cathode current collector was revealed to be by-product of molten salt electrolyte decomposition. In particular, the result showed that the Ni-Al alloys (Al3Ni2, Ni3Al and Al3Ni) were electrochemically deposited on graphite current collectors in line with over-discharging behaviors. It is assumed that the NiCl2 solubility in molten salt electrolytes leads to the co-deposition of Ni-Al alloys by increasing metal deposition potential above 1.6 V (vs. Na/Na+). The cell tests have revealed that the composition of molten salt electrolytes modified by various additives makes a decisive influence on the over-discharging behaviors of the cells. It was revealed that NaOCN addition to molten salt electrolytes was advantageous to suppress over-discharge reactions by modifying the characteristics of molten salt electrolytes. NaOCN addition into molten salt electrolytes seems to suppress Ni solubility by maintaining basic melts. The cell using modified molten salt electrolyte with NaOCN (Cell D) showed relatively less cell degradation compared with other cells for long cycles