Porous TiO2 coating containing calcium and phosphate was prepared on Ti6Al4V alloy substrate using micro-arc oxidation, which was termed as MAO. And the MAO coating was treated by alkali and annealing, which was termed as MAONH. The morphology, element content and phase composition of the two kinds of coatings were analyzed by SEM, EDS and XRD, respectively. The results show that the MAONH coating is mainly composed of anatase, rutile and CaTiO3 phases, which is very different from the MAO coating. It is found that Ca2+ and P5+ ion deposit on the MAONH coating more easily than that on the MAO coating. The reason could be the hydrolysis of CaTiO3 soaking in Hank’s solution, which results in abundant Ca2+ and OH- ions. The apatite is deposited on the MAONH coating by ionic exchanges between OH-, Na+ ions of the MAONH coating and Ca2+, PO43- ions in the Hank’s solution.