•γ-ray irradiation caused more Cs+ leaching out from geopolymer wasteform.•Pore structure change induced by irradiation caused the increase of leachability.•Fly-ash-based geopolymer is a potential material for radionuclide immobilization.Leaching of simulated 133Cs+ radionuclides from geopolymer wasteforms was examined with regard to effects from gamma-ray irradiation. Specifically, the compressive strengths, microstructures, pore structures, and leaching resistance of geopolymer wasteforms before and after irradiation were characterized. The leaching experiments were performed by immersion of wasteforms in deionized water, ground water, and seawater. It was found that gamma rays did not produce significant morphological changes, except for changes in the pore size distribution. The cumulative leaching fraction of all the leachants from the irradiated samples increased relative to the non-radiated samples, particularly during long leaching periods (11–42 days). These results, and those from a mercury intrusion porosimeter analysis, can be attributed to irradiation-induced changes in pore structure. All the leaching indexes were greater than the minimum acceptable value of 6.0 set by the American Nuclear Society Standards committee, which indicated that the fly-ash geopolymers are suitable for radionuclide immobilization. However, the effects of gamma-ray irradiation on the immobilization of radionuclides cannot be ignored.