Highly oriented hydroxyapatite coatings (HACs) were obtained on titanium substrates through a radio-frequency thermal plasma spraying (TPS) method. XRD patterns showed that the HACs had crystallites with [001] preferred orientation vertical to the coating's surface. XRD results also indicated that tetracalcium phosphate crystallites in the as-sprayed HAC were oriented in the (100) direction. XRD peaks corresponding to tetracalcium phosphate, tricalcium phosphate and calcium oxide were absent after heat and hydrothermal treatment. The orientation degree of the HAC was influenced little by such post-heat treatments. Considering the crystallographic relationship between the tetracalcium phosphate in the as-sprayed HAC and the HA crystallites formed in the heat-treated HAC, these XRD results indicate that the tetracalcium phosphate in the as-prepared coatings transformed topotaxially into HA during the post-heat treatment. TEM and SEM analyses of the highly oriented HAC were conducted. The characteristic lamellar structure of TPS deposits was observed in cross-sections of the HAC. A prismatic texture was also observed in magnified SEM images. TEM observation showed that 200-800-nm-wide prismatic crystallites were formed in HA splats, and their longitudinal axis was oriented vertically to the coating's surface. SAD patterns showed that the longitudinal axis of the prismatic crystallites corresponded to the [001] zone axis of the HA crystal.