Three hydroxyapatite bioceramics incorporating either titanium(IV) and fluoride, or titanium(IV), fluoride and salicylate have been prepared. Each bioceramic was analysed using XPS, ToF-SIMS, X-ray powder diffraction, ³¹P/¹⁹F MAS solid state NMR and Diffuse Reflectance FTIR spectroscopic techniques. The results acquired suggest that titanium(IV) substitutes for calcium, and fluoride substitutes for hydroxide ion within the HA matrix, the two processes being essentially independent. Data obtained also reveal a greater incorporation of titanium(IV) in the bioceramic containing titanium, fluoride and salicylate.