A series of Ag-doped hydroxyapatite (Ag-HA) of the general molecular formula (Ca10-xAgx(PO4)6(OH)2), where x = 0, 0.4, 0.8, 1.2, and 1.6 mole had been prepared by a solution technique. X-ray diffraction (XRD), Fourier transform infrared spectrometry (FTIR), Transmission electron microscope (TEM), Electron diffraction (EDP) and Scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDS) were used for assigning the presence of glass-ceramic, crystalline, and polycrystalline phases. Addition of low content of silver to the HA leads to the formation of beta-tricalcium phosphate (β-TCP) and Ag-HA. The spectral changes were directly dependent on Ag concentration, time, and heat treatment temperature. The results revealed the occurrence of different functional groups of HA and β-TCP in the matrices of the glass-ceramic. The role of the nucleating agent Ag was critically assigned and the presence of the characteristic phases of HA and β-TCP was confirmed and properly assigned and addressed. TEM and SEM were used to properly assign the morphology of the formed phases. Ag-HA prepared with β-TCP components can be used as unique bio-ceramic materials in different biological applications.