The effect of minor addition of calcium to lithium anode on the electrochemical behavior of lithium anode in 4M LiOH at 30°C temperature is investigated by hydrogen collection, polarization curves and electrochemical impedance spectroscopy. The results show that the hydrogen evolution rate is marginally reduced with increasing calcium content. Addition of calcium to lithium mainly inhibits the anodic process. Minor addition of calcium to lithium slightly reduced the discharge current of lithium anode. Minor addition of calcium to lithium anode marginally enhances the hydrogen inhibition of lithium by the formation of calcium hydride combined with LiOH and LiOH·H2O formed on the anode surface.