Nano-structured hydroxyapatite (HA) coatings were deposited on the Ti-6Al-4V alloy substrate by the liquid precursor plasma spraying (LPPS) process. The thermal behavior of the HA liquid precursor was analyzed to interpret the phase change and structure transformation during the formation process of the nano-structured HA coatings. The phase composition, structure and morphology of the nano-structured HA coatings were characterized by x-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transform infrared (FTIR) spectroscopy. The XRD spectra showed that the coatings deposited by the LPPS process mainly consisted of the HA phase and the crystallite size was measured to be 56 nm. The SEM observation showed that the as-deposited LPPS coatings had small splat size, and nano-scale HA particles were found in certain regions of the coating surface. The FTIR spectroscopy showed the strong presence of the OH(-) group in the as-deposited LPPS coatings, indicating a superior structural integrity. In addition, the coatings deposited by the LPPS process were also carbonated HA coatings. The results indicate that the LPPS process is a promising plasma spraying technique for depositing nano-structured HA coatings with unique microstructural features that are desirable for improving the biological performance of the HA coatings.