Ce₂[Zr_1-x(Mg_1/3Sb_2/3)_x]₃(MoO₄)₉ (0.02 ≤ x ≤ 0.10) ceramics were prepared by the traditional solid-state method. A single phase, belonging to the space group of $R\overline{3}c$, was detected by using X-ray diffraction at the sintering temperatures ranging from 700 to 850 ℃. The microstructures of samples were examined by applying scanning electron microscopy (SEM). The crystal structure refinement of these samples was investigated in detail by performing the Rietveld refinement method. The intrinsic properties were calculated and explored via far-infrared reflectivity spectroscopy. The correlations between the chemical bond parameters and microwave dielectric properties were calculated and analyzed by Phillips-van Vechten-Levine (P-V-L) theory. Ce₂[Zr_0.94(Mg_1/3Sb_2/3)_0.06]₃(MoO₄)₉ ceramics with excellent dielectric properties were sintered at 725 ℃ for 6 h (ε_r = 10.37, Q×f = 71,748 GHz, and τ_f = -13.6 ppm/℃, ε_r is the dielectric constant, Q×f is the quality factor, and τ_f is the temperature coefficient of resonant frequency).