Bi is one of important alloying elements in aluminum anode of alkaline batteries. In this work, Al–Bi alloy is used as anode material. And how to optimize the addition amount of Bi in aluminum anode was studied to improve the discharge performance of aluminum anode. Using 4 mol · L−1 NaOH solution as an electrolyte, the electrochemical properties of Aluminum anode Al–xBi (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0 wt%) with different Bi content were studied. The results show that the addition of Bi will destroy the passivation film on the surface of aluminum alloy, making the reaction further. The addition of Bi element has the effect of refining grain and homogenizing microstructure and reduces the solution resistance and polarization resistance during discharge to a certain extent. Under the condition of 4 mol · L−1 NaOH solution as the electrolyte, the Al–0.8Bi anode plate has better corrosion resistance and electrode activity compatibility.