The effect of cerium as an inhibitor on the discharge and hydrogen evolution at a lithium anode in alkaline electrolyte with additives was evaluated. The electrochemical behaviors of lithium and lithium–cerium alloy are assessed by hydrogen evolution collection, discharge current density, anodic potential, XRD (X-ray diffraction) and scanning electron microscope (SEM). For these conditions, the results show that minor addition of cerium to lithium decreased the hydrogen evolution on the surface of lithium–cerium alloy in an alkaline electrolyte containing corrosion inhibitors. SEM and XRD observation showed that the slow dissolution of lithium–cerium alloy generates the formation of LiOH, LiOH·H2O and Ce(OH)3. The lithium–cerium surface is less porous than the lithium surface. Hydrogen evolution decrease, prompted by adding cerium to lithium, which is related to reduced porosity of the film enhanced by Ce(OH)3.