Perovskite-based ceramic composites were developed as potential waste form materials for immobilizing cesium (Cs) and iodine (I) with high waste loadings and chemical durability. The perovskite Cs₃Bi₂I₉ has high Cs (22 wt%) and I (58 wt%) content, and thus can be used as a potential host phase to immobilize these critical radionuclides. In this work, the perovskite Cs₃Bi₂I₉ phase was synthesized by a cost effective solution-based approach, and was embedded into a highly durable hydroxyapatite matrix by spark plasma sintering to form dense ceramic composite waste forms. The chemical durabilities of the monolithic Cs₃Bi₂I₉ and Cs₃Bi₂I₉–hydroxyapatite composite pellets were investigated by static and semi-dynamic leaching tests, respectively. Cs and I are incongruently released from the matrix for both pure Cs₃Bi₂I₉ and composite structures. The normalized Cs release rate is faster than that of I, which can be explained by the difference in the strengths between Cs–I and Bi–I bonds as well as the formation of insoluble micrometer-sized BiOI precipitates. The activation energies of elemental releases based on dissolution and diffusion-controlled mechanisms are determined with significantly higher energy barriers for dissolution from the composite versus that of the monolithic Cs₃Bi₂I₉. The ceramic-based composite waste forms exhibit excellent chemical durabilities and waste loadings, commensurate with the state-of-the-art glass-bonded perovskite composites for I and Cs immobilization.