The effects of adding cerium to lithium on the properties of lithium anode were studied in alkaline aqueous LiOH electrolyte at 30 °C. Self-corrosion hydrogen evolution rate at open circuit potential and electrochemical experiments show that the magnitude of hydrogen evolution rate is reduced obviously by adding cerium to lithium. As the content of Ce increases to 0.08 wt%, the inhibition efficiency reaches approximately 83.3%. SEM results show that the surface of Li-Ce alloy forms more compact and less porous film than that of pure lithium after discharge. XRD examination proves the presence of Ce(OH)3 in the lithium-cerium alloy film besides LiOH and LiOH·H2O. It is suggested that Ce(OH)3 plays a key role in inhibiting the hydrogen evolution and affecting discharge potential on the surface of lithium-cerium alloy anode in aqueous alkaline LiOH electrolyte.