The latter provides not only control over facet stabilization and then shape for the first time, it also enables phase selection. The water content also seems to offer the ability to tune the crystallization pathway of Mn(V) hydroxyapatites, switching between liquid-phase and solid-state crystallization mechanisms, with a large impact on the control of the nanostructure. By defining the acid-baseredox stability window of a Mn(V) hydroxyapatite in alkaline media, we demonstrate that hydrofluxes are a versatile platform, which offers materials standing strongly oxidative conditions.