AbstractManufacturing aqueous batteries based on the magnesium cations is an important step towards more sustainable and safer energy storage solutions. Thus, it is important to understand how these systems age and which species are formed throughout numerous charge/discharge cycles. To this end, we have used radiolysis to induce accelerated ageing in concentrated aqueous solutions of magnesium bistriflimide Mg(TFSI)2 (also called “water‐in‐salt electrolytes” or WISEs). We demonstrate in this work that the degradation products formed, whether in the gas or liquid phase, are very similar to those formed in concentrated LiTFSI aqueous solutions. In fact, the behavior under ionizing radiation is driven by the anion/water molar ratio regardless of whether the cation is Li+ or Mg2+. This is because both cations are non‐reactive, and the bond strengths in the TFSI− anion do not vary with the nature of the cation. Reaction mechanisms are proposed to explain the formation of several species under ionizing radiation.