LiMnPO4 (LMP) microwave dielectric ceramics were manufactured at different temperatures via a standard solid-state reaction method, and the LMP ceramic sintered at 750 °C displayed dielectric properties of εr = 7.82, Q × f = 29,189 (f = 12.7 GHz). The lattice vibrational characteristics of LMP ceramics were studied utilizing both infrared reflection and Raman scattering spectroscopy to clarify the basic principle of the dielectric response. The intrinsic properties that were fitted and simulated based on the infrared spectra agreed with the measured property values. The low-frequency vibrational modes contributed more to the dielectric properties than the high-frequency modes. Upon increasing the temperature, the permittivity was positively correlated with the bond length but showed the opposite trend of the Raman shift of mode 9 Ag(υ1). The Q × f value was positively correlated with the packing fraction but negatively correlated with the FWHM of mode 10 Ag(υ3). Thus, the structure-property relationships of LMP ceramics were established as a function of sintering temperature.