Ce 2 [Zr 1-x (Mg 1/3 Sb 2/3 ) x ] 3 (MoO 4 ) 9 (0.02≤x≤0.10) ceramics were prepared well through the traditional solid-state method. A single phase, belonging to the space group of R-3c, was detected by using X-ray diffraction at sintering temperatures ranging from 700 to 850 °C. The crystallization micro-structural of specimens was examined by applying Scanning electron microscopy. The structural 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 bonds parameters and microwave dielectric properties were calculated and analyzed by P-V-L theory. Ce 2 [Zr 0.94 (Mg 1/3 Sb 2/3 ) 0.06 ] 3 (MoO 4 ) 9 ceramics with excellent dielectric properties: ε r = 10.37, Q×f = 71748 GHz and τ f = −13.6 ppm/°C sintered at 725 °C for 6 hours.