The properties of composite coatings formed by plasma electrolytic oxidation (PEO) were affected by the alloy composition. The corrosion resistance and apatite-forming ability of PEO coatings formed on Mg–6Al–1Zn–xCa alloys with a variation of Ca content were investigated. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements showed an order magnitude improvement of corrosion resistance in the AZ61 alloy as a result of the coating. A higher enhancement in polarization resistance was obtained in the Mg–6Al–1Zn–1Ca and Mg–6Al–1Zn–2Ca alloys due to thicker coatings were formed as a result of the incorporation of calcium oxide/hydroxide. However, the underlying substrates were more prone to localized corrosion with increasing Ca content. The microstructure investigation revealed an enlargement in precipitates (Al2Ca, Mg2Ca) sizes with increasing Ca content in the alloys. The growth of larger size precipitates increased the danger to micro galvanic corrosion. Apatite layers were formed on all of the coatings indicating high apatite-forming ability, but the layers formed on the Mg–6Al–1Zn–1Ca and Mg–6Al–1Zn–2Ca alloys contained higher Mg, possibly due to the accumulation of corrosion product, than that on the Mg–6Al–1Zn alloy. The alloying element Ca should be limited to 1 wt.% as the excess tended to degrade the corrosion resistance and apatite-forming ability of the PEO coating.