The oxysilicate apatite host CaLa₄(SiO₄)₃O has been explored for immobilization of radioactive nuclides. Divalent ion, trivalent rare earth ion, and combined ionic substitutions in the silicate oxyapatite were carried out to optimize the simulated wasteform composition. The phases were characterized by powder X-ray diffraction, FT-IR, TGA, SEM-EDS, and HT-XRD techniques. The results revealed the effect of ionic substitutions on the structure and thermal expansion behavior. The investigation resulted in the formulation of simulated wasteforms such as La_3.4Ce_0.1Pr_0.1Nd_0.1Sm_0.1Gd_0.1Y_0.1(SiO₄)₃O (WF-1) and Ca_0.8Sr_0.1Pb_0.1La_3.4Ce_0.1Pr_0.1Nd_0.1Sm_0.1Gd_0.1Y_0.1(SiO₄)₃O (WF-2). In comparison to the average axial thermal expansion coefficients of the hexagonal unit cell of the parent CaLa₄(SiO₄)₃O measured in the temperature range 298–1073 K (α′_a = 9.74 × 10^–6 K^–1 and α′_c = 10.10 × 10^–6 K^–1), rare earth ion substitution decreases the thermal expansion coefficients, as in the case of La_3.4Ce_0.1Pr_0.1Nd_0.1Sm_0.1Gd_0.1Y_0.1(SiO₄)₃O (α′_a = 8.67 × 10^–6 K^–1 and α′_c = 7.94 × 10^–6 K^–1). However, the phase Ca_0.8Sr_0.1Pb_0.1La_3.4Ce_0.1Pr_0.1Nd_0.1Sm_0.1Gd_0.1Y_0.1(SiO₄)₃O shows an increase in the values of thermal expansion coefficients: α′_a = 11.74 × 10^–6 K^–1 and α′_c = 11.70 × 10^–6 K^–1.