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In this fundamental solid-state chemistry study, two sample series were investigated in depth: iron(III)-doped hydroxyapatite (HA) compounds obtained from a co-sintering process of hematite and pure HA under air and iron(III)-doped HA compounds obtained from a co-sintering process from iron(II) acetate and pure HA under an argon atmosphere. X-ray diffraction, UV-visible, Fourier transform infrared, 1 H and 31 P NMR, electron paramagnetic resonance (EPR,) and Mössbauer spectroscopy methods were coupled to unravel the Fe valence states, the interactions with other anionic species (OH - and PO 4 3- ), and finally the complex local environments in hexagonal channels in both the series. In particular, we highlighted the associated mechanism to ensure electroneutrality with a focus on deprotonation versus calcium substitution. By diverging mechanisms, Fe 3+ and Fe 2+ ions were found to be located in different coordinated sites: 4(+1) coordinated site for Fe 3+ and 2(+3) coordinated site for Fe 2+ and clearly associated with very different Mössbauer and EPR signatures as various absorption bands (leading to different sample colors).