The stability of cementitious materials under the harsh environment they will experience when used for radioactive waste disposal is incredibly important. Therefore, understanding the irradiation resistance of geopolymer cement, a potential alternative binder for the treatment of nuclear waste, is of the utmost importance when trying to develop a safety case for these materials. The study presented here addresses the structural and chemical changes of metakaolin‐based geopolymers, designed with different water contents, and exposed to a total cumulative dose of 1 MGy of gamma radiation. The range of formulations that were tested showed a significant loss of free water related to the irradiation process, which has led to an increase in the porosity. Analysis of the chemical structure has shown minimal changes in the main binding type‐gel phase, demonstrating high microstructural stability. Results showed that in samples cured for longer than 20 h, the bound/gel structure water remained in the sample when the water content was kept low enough. As the porosity and water content increase, more gel water is removed due to radiation exposure. However, the degree to which the water is removed from the gel structure is very small, and minimal changes can be seen across the geopolymers tested. Overall, metakaolin‐based geopolymers appear resistant to irradiation up to 1 MGy, which offers a potentially viable alternative for the immobilization of problematic intermediate‐level waste.