Ti-6Al-4V alloys are mainly used as dental materials due to their excellent biocompatibility, corrosion resistance, and chemical stability. However, they have a low bioactivity with bioinertness in the body. Therefore, they could not directly bond with human bone. To improve their applications, their bone bonding ability and bone formation capacity should be improved. Thus, the objective of this study was to improve the bioinert surface of titanium alloy substrate to show bioactive characteristics by performing surface modification using wollastonite powder. Commercial bioactive wollastonite powder was successfully deposited onto Ti-6Al-4V alloy using a room temperature spray process. It was found that wollastonite- coated layer showed homogeneous microstructure and uniform thickness. Corrosion resistance of Ti-6Al-4V alloy was also improved by plasma electrolytic oxidation treatment. Its wettability and bioactivity were also greatly increased by wollastonite coating. Results of this study indicate that both plasma electrolytic oxidation treatment and wollastonite coating by room temperature spray process could be used to improve surface bioactivity of Ti-6Al-4V alloy substrate.