Structural and microstructural investigation of solution precursor plasma sprayed copper-doped hydroxyapatite coatings with different Cu dopant concentration was carried out. Scanning electron micrographs did not show any significant morphological changes at the surface and cross-section of the coatings as copper content increases. X-ray diffraction results showed the decrease in the HA phase content from 93 wt.% to 14 wt.% and its degree of crystallinity from 94% to 85% with increasing copper concentration. Raman and IR spectra revealed the broadening and red-shifting of the phosphate bands due to the distortion of the HA structure caused by possible insertion of copper. X-ray photoelectron spectroscopy identified Cu and Cu2+ as copper species incorporated in HA. Rietveld refinement showed an increase in the lattice a and c parameter and expansion of the unit cell volume associated to an interstitial insertion of Cu along the hexagonal channel of the HA structure.