1 − x)CaTiO 3 -xLa(Mg 2/3 Nb 1/3 )O 3 (CT-LMN; x = 0-1.0) solid solutions were prepared by a solid-state reaction method. A phase transition from a disordered orthorhombic (Pbnm) structure to a 1:1 ordered monoclinic (P21/n) structure was observed when x increased from 0.5 to 0.6. Some new parameters, such as ionic polarizability in a polyhedron and ionic packing fraction in a polyhedron, were defined to explain the structure-property relationships of CT-LMN ceramics based on the Rietveld refinement results. The measured dielectric constant (ε r-mea ) decreased monotonically with B-site ionic polarizability in the [BO 6 ] octahedron (𝛼 T D (B)∕𝑉 [B] ) when the x value increased from 0 to 1.0. The quality factor (Qf) was dominated by the packing fraction of B-site cations in the [BO 6 ] octahedron (PF [B] ), and both presented an increasing trend. The temperature coefficient of resonant frequency (τ f ) decreased from +588.5 to −79.7 ppm/ • C, and it was highly correlated to the tolerance factor (t), 𝛼 𝑇 𝐷 (B)∕𝑉 [B] and PF [B] . The highest Qf value is obtained at x = 1.0 when sintered at 1600 • C for 10 h with ε r = 23.65 ± 0.2, Qf = 33517 ± 2000 GHz (@7.8 GHz), and τ f = −79.7 ± 2.0 ppm/ • C. Moreover, a near-zero τ f value was achieved at x = 0.4 with ε r = 43.52 ± 0.2, Qf = 17239 ± 2000 GHz (@5.2 GHz), and τ f = −10.2 ± 2.0 ppm/ • C.