Micro-plasma oxidation (MPO) technique is a new technique by which compound ceramic coating can be grown in situ on Al, Ti, Mg and many other valve-metals. Compound ceramic coatings on Ti-6Al-4V alloy were prepared for different time by pulsed bi-polar MPO in NaAlO2 solution. The phase composition, morphology and the element distribution of the coatings were studied by XRD, SEM and JEOL SUPERPROBE 733 electric probe, respectively.Electrochemical Impedance Spectra (EIS) of the coatings were measured to study the structure character of the coatings.Through the proper EIS interpreting software, the "equivalent circuit" of the coatings was established, and the fitting values of equivalent element were calculated. The coating is mainly composed of Al2TiO5, α-Al2O3 and rutile TiO2. The content of Ti element in the coating is less than that of substrate; its distribution is relatively uniform, and Ti in the outer layer is less than that in the inner layer. The content of Al in the coating is more than that of substrate, and its distribution is not even: Al in the middle part is more than that on both sides of the coating; And the EIS analysis has illustrated the double-layer structure of the coatings, and the outside layer is loosen and the inner layer compact; with the increase of the oxidizing time,the surface roughness of the coatings, and the porosity of the outer layer of the coating are increased while the compactness of the inner layer of the coatings are improved.