The electrochemical behavior of lithium in lithium hydroxide solution with sodium nitrite has been investigated in this paper. The results show that the hydrogen evolution rate decreases with increasing sodium nitrite concentration. Through potentiostatic polarization and scanning electron microscope (SEM), we found that the current efficiency keeps nearly unchanged with sodium nitrite introduction to the solutions. The porosity of the lithium surface film decreased due to the precipitation of LiOH promoted by sodium nitrite.