Plasma electrolytic oxidation (PEO) has drawn attention and been studied intensively all through the world. The thick ceramic coatings fabricated by the technique exhibit excellent properties, including hardness and wear resistance, thermal and electrical insulation, and corrosion resistance, due to the characteristic phase composition and microstructure of the coating layers. However, most of the studies have dealt with manufacturing process itself and the apparent properties of coating layers and researches on the microstructural basis including transmission electron microscopy analysis are limited so far. In this investigation, a basic approach to PEO process was tried, adapting time-potential behavior analysis under constant current mode (galvanostatic) oxidation, and microstructural analysis on the coating structure, including X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The time-potential behavior analysis under constant current DC was carried out, and the resultant evolution of the microstructure was characterized..