Compound ceramic coatings with the main crystalline of Al2TiO5 (as-coated samples) were prepared on Ti-6Al-4V alloy by pulsed bi-polar micro-plasma oxidation (MPO) in NaAlO2 solution. The coated samples were calcined in Ar and air at 1000oC, respectively. The phase composition, morphology and element content of the coatings were investigated by XRD, SEM and XRF. The samples treated in Ar and the as-coated ones were calcined in air at 1000oC to study the oxidation resistance of the samples. The results showed that Al2TiO5 decomposed and transformed into corundum and rutile TiO2 during the high temperature calcination. Al2TiO5 decomposed very quickly in air and the proportion of Al2O3 to TiO2 was 44:55 after a complete decomposition. On the contrary, Al2TiO5 decomposed very slowly in argon with the final proportion of Al2O3 to TiO2 of 81:18 on the coating surface. The morphology of the ceramic coatings after the calcination was also different. The coatings calcined in argon were fined: the grains and pores were smaller than those of the coatings calcined in air. The weight gains of both coatings changed in the form of parabola law, and the weight gains of the coated samples treated in argon were comparatively lower than that of the as-coated samples. During the high temperature calcination, the samples treated in argon cannot distort easily, compared with the as-coated ones.