Oxide coatings are formed on die-cast AZ91D Mg alloy through an environmentally friendly plasma electrolytic oxidation(PEO) process using an electrolytic solution of NaAlO2, KOH, and KF. The effects of PEO condition with different duty cycles (10 %, 20 %, and 40 %) and frequencies(500 Hz, 1,000 Hz, and 2,000 Hz) on the crystal phase, composition, microstructure, and micro-hardness properties of the oxide coatings are investigated. The oxide coatings on die-cast AZ91D Mg alloy mainly consist of MgO and MgAl2O4 phases. The proportion of each crystalline phase depends on various electrical parameters, such as duty cycle and frequency. The surfaces of oxide coatings exhibit as craters of pancake-shaped oxide melting and solidification particles. The pore size and surface roughness of the oxide coating increase considerably with increase in the number of duty cycles, while the densification and thickness of oxide coatings increase progressively. Differences in the growth mechanism may be attributed to differences in oxide growth during PEO treatment that occur because the applied operating voltage is insufficient to reach breakdown voltage at higher frequencies. PEO treatment also results in the oxide coating having strong adhesion properties on the Mg alloy. The micro-hardness at the cross-section of oxide coatings is much higher not only compared to that on the surface but also compared to that of the conventional anodizing oxide coatings. The oxide coatings are found to improve the micro-hardness with the increase in the number of duty cycles, which suggests that various electrical parameters, such as duty cycle and frequency, are among the key factors controlling the structural and physical properties of the oxide coating.