The effects of zinc oxide and/or polyethylene glycol (PEG) as electrolyte additives on the corrosion and electrochemical performances of pure aluminum in 4.0 M KOH solutions were investigated by means of hydrogen collection, polarization curve, galvanostatic discharge, scanning electron microscopy (SEM), and energy dispersive analysis of X-ray (EDAX). The addition of ZnO markedly inhibited the corrosion of aluminum in 4.0 M KOH solutions, resulting from the deposition of zinc with high hydrogen evolution overpotential in aluminum surfaces. The introduction of PEG in the alkaline zincate solution obviously improved the deposition of zinc by increase in the overpotential of zinc deposition, thus the corrosion rate of aluminum in the alkaline zincate solutions with PEG was further decreased. The enhancement effect of PEG on the inhibition of zinc oxide first increased and then decreased with increasing the content of PEG in the electrolyte. The electrolyte system with 0.2 M ZnO and 2.0 mM PEG presented the highest inhibition efficiency (98.8%) for the corrosion of aluminum. The results of galvanostatic discharge indicated that the aluminum anode shows excellent discharge performances in the 4.0 M KOH solution with 0.2 M ZnO and 2.0 mM PEG.