Ion release of Mg- and Zn-substituted Bioglass 45S5 (46.1 SiO2-2.6 P2O5-26.9 CaO-24.3Na2O; mol%; with 0, 25, 50, 75 or 100% of calcium replaced bymagnesium/zinc) was investigated at pH 7.4 (Tris buffer) and pH 4 (acetic acid/sodium acetate buffer) in static and dynamic dissolution experiments. Despite Mg2+ and Zn2+ having the same charge and comparable ionic radii, they influenced the dissolution behaviour in very different ways. In Tris, Mgsubstituted glasses showed similar ion release as 45S5, while Zn-substituted glasses showed negligible ion release. At low pH, however, release behaviour was similar, with all glasses releasing large percentages of ions within a few minutes. Precipitation of crystalline phases also varied, as Mg- and Zn-substitution inhibited apatite formation, and Zn-substitution resulted in formation of zinc phosphate phases at low pH. These results are relevant for glasses used in aluminium-free glass ionomer bone cements, as they show that Zn/Mg-substituted glasses release ions similarly fast as glasses containing no Zn/Mg, suggesting that these ions are no prerequisite for ionomer glasses. Zn-substituted glasses may potentially be used as controlled-release materials, which release antibacterial zinc ions when needed only, i.e. at low pH conditions (e.g. bacterial infection), but not at normal physiological pH conditions.