AbstractCommercially pure Fe, Fe35Mn, and (Fe35Mn)5Ag alloys were prepared by uniaxial pressing of the mixture of individual powders, followed by sintering. The influence of the alloying elements Mn and Ag on the corrosion behaviour of these Fe-based alloys was investigated in Hanks’ Balanced Salt Solution (HBSS). Furthermore, the role of the components in HBSS, particularly Ca2+ ions during alloys degradation was studied. Distribution of local pH and dissolved oxygen concentration was measured 50 μm above the interface of the degrading alloys. The results revealed that 5 wt% Ag addition to Fe35Mn alloy triggered micro-galvanic corrosion, while uniform corrosion dominated in pure Fe and Fe35Mn. Fast precipitation of Ca–P-containing products on the surface of these Fe-based alloys buffered local pH at the metal interface, and blocked oxygen diffusion at the initial stages of immersion. In the (Fe35Mn)5Ag, the detachment or structural changes of Ca–P-containing products gradually diminished their barrier property. These findings provided valuable insights into the degradation mechanism of promising biodegradable Fe-based alloys.