Silver-doped hydroxyapatite (Ag-doped HA) nanopowders were synthesized using calcium hydroxide (Ca(OH)2), phosphorus pentoxide (P2O5) and silver nitrate (AgNO3) precursors, through a one-pot mechanochemical process. The influence of dopant content on the phase formation, structural properties and morphological features was examined. The results showed that the as-prepared powders were single-phase hexagonal HA in the absence of the dopant. With the addition of the dopant, a similar phase structure was achieved, however some changes were observed with regards to the peak position and broadening. With the increase of Ag substitution, some alterations in the structural features of the milled powders were observed, where the crystallite size, lattice strain and crystallinity degree were between 25 ± 18 and 33 ± 14nm, between 0.486 ± 0.0.161 and 0.824 ± 0.477, and between ~ 83 and 93%, respectively. From the Fourier transformed infrared (FTIR) spectroscopy spectra, the location of the CO3-derived bands revealed that the replacement of PO43− by CO32− (B-type) was dominant in the Ag-doped HA nanopowders. This facile solid-state method is an alternative process for the preparation of bioceramic nanopowders. Display omitted •Ag-doped HA nanopowders were synthesized by a one-pot mechanochemical treatment.•Morphological and structural features were examined as a function of dopant content.•Spheroidal particles showed an average size of 32 ± 1nm in the case of Ag-doped HA.•Unit cell volume unpredictably decreased due to the vacancy induced lattice relaxation.