An inadvertent leakage of 90 Sr into the environment can induce an easy accumulation in biosphere and cause a continuous radiation to the surrounding ecosystem. In this study, sodium hexametaphosphate (Na 6 O 18 P 6 ) was employed to modify the blast furnace slags (BFS) to enhance the chemical stabilization of Sr 2+ ions in the BFS-based cementitious materials. Microwave irradiation (MW) was used to further increase the binder activity of BFS samples and strengthened the mechanical strengths and durability of BFS-based blocks. A combination of experimental factors including the mass ratio of Na 6 O 18 P 6 to BFS–Sr 0.1 of 15%, the ratio of solid to liquid of 1:4 mg/L, the output power of 650 W, and the activation time of 3 min was most conductive to achieving an optimal microwave-irradiation process. Four extraction solutions were sorted by their leaching abilities following as MgSO 4 solution > H 2 SO 4 solution > CH 3 OOH solution > deionized (DI) water based on their leaching results. Compared with microwave irradiation, an addition of Na 6 O 18 P 6 to BFS samples obtained a better compressive strength for BFS-based blocks. However, a microwave-irradiation treatment was more effective in improving the resistances of blocks to gamma irradiation and thermal-thaw changes. Exposing to gamma irradiation over 6 months and enduring to thermal-thaw tests over 15 cycles, the microwave-treated blocks only lost 3.29% and 2.23% of leaching removal efficiencies in deionized water, respectively. Microwave irradiation increased the mechanical strengths of BFS-based blocks and inhibited leaching of Sr 2+ ions from matrices mainly by strengthening hydration reactions and Sr 2+ encapsulation.