Compound ceramics coatings on the Ti-6Al-4V alloy were prepared by the direct current micro-plasma oxidation (MPO) in NaAlO2 solution. The composition and morphology of the coatings were studied with the X-ray diffraction (XRD) and the scanning electron microscopy (SEM), respectively. Inductively coupled plasma atomic emission spectrometer technique was used to analyze the solution features of Ti-6Al-4V alloy in the process of preparation. The results reveal that Al2TiO5 forms in the coatings at the initial stages of MPO reaction, and its content changes rapidly with the reaction continuing: after 20 min, the ceramics coatings are composed of α-Al2O3, γ-Al2O3 and Al2TiO5, but after 40 min, its main composition is of α-Al2O3. The content of Ti in the solution will increase when the MPO time extends, and as will Al in the anode area until, after 30 min, it reaches the maximum and keeps constant from then on. Both substrata of Ti and Al in the electrolyte join the MPO reaction at the initial stage, where the formation of Al2TiO5 happens; but as the MPO reaction prolongs, more and more Al in the electrolyte will take part in the reaction, leading to the appearance of a large amount of Al2O3.