Plasma electrolytic oxidation (PEO) of cast A356 aluminum alloy was carried out in 32 g/L NaAlO₂ with the addition of different concentrations of NaOH. The stability of the aluminate solution is greatly enhanced by increasing the concentration of NaOH. However, corresponding changes in the PEO behaviour occur due to the increment of NaOH concentration. Thicker precursor coatings are required for the PEO treatment in a more concentrated NaOH electrolyte. The results show that the optimal NaOH concentration is 5 g/L, which improves the stability of storage electrolyte to about 35 days, and leads to dense coatings with high wear performance (wear rate: 4.1×10^-7 mm³·N^-1·m^-1).