Mg3(VO4)2 (MVO) microwave dielectric ceramics were fabricated by a conventional solid-state sintering method at different sintering temperatures (Ts) between 1000 °C and 1100 °C. The effects of Ts on the phase evolution, the crystal structures, the dielectric responses, and the lattice vibrational characteristics of MVO were investigated. XRD patterns after Rietveld refinement were applied to analyze the phase evolution and the crystal structures of the samples, which shows the orthorhombic structure with the space group of Cmca for the MVO ceramics. Micrograph from scanning electron microscopy shows a uniform and dense crystal structure with the highest bulk density for the MVO sample sintered at 1050 °C. Raman scattering spectroscopy and infrared reflectance spectroscopy were used to dissect the lattice vibrational characteristics of the MVO ceramics. There are two types of vibrational modes of the MVO samples, i.e., the external modes caused by the deformation of VO43- and the rotational and translational vibrations of the lattices, the internal modes attributed to the asymmetric stretching vibrations of V-O bonds. The intrinsic dielectric properties were determined by fitting the data with a four-parameter semi-quantum (FPSQ) model. Modes 1, 2, and 4, associated with the external modes, have the greatest contribution coefficient of 65.58% to the dielectric constant, and Mode 1 has the greatest contribution coefficient of 51.40% to the dielectric loss. The structure-property relationships were semi-quantitatively mathematically established according to the Raman modes. The MVO sample sintered at 1050 °C has the best dielectric properties of εr = 9.59 and Q × f = 41,193 GHz (f = 13.69 GHz). •Mg3(VO4)2 microwave dielectric ceramics of crystal structures, dielectric properties, and phonon characteristics were studied.•The lattice vibrational characteristics were analyzed utilizing Raman and infrared reflection spectroscopy.•The physical mechanism of the dielectric response was clarified.•Relationships of structures-properties were established using Raman active modes as a media.