Ceramic coatings with the main crystalline of TiO2 were prepared on Ti-6Al-4V alloy by pulsed bi-polar Micro-arc Oxidation (MAO) in Na2SiO3 solution. The coated samples were calcined in argon under 1000oC. The phase composition, morphology and element content of the ceramic coatings were investigated by XRD, SEM and EDS. The results showed that the main components of the coatings are TiO2 and amorphous substances, after oxidation in argon, SiO2 was crystalized in coating. The content of elements in the coatings both changed a little.