In this work, Zn-Ni co-modified LiMg0.9Zn0.1-xNixPO4 (x = 0–0.1) microwave dielectric ceramics were fabricated using a solid state synthesis route. Rietveld refinement of the XRD data revealed that all ceramic samples have formed a single phase with olivine structure. SEM images showed that the samples have a dense microstructure, that agrees with the measured relative density of 97.73 %. Based on the complex chemical bond theory, Raman and infrared reflectance spectra, we postulate that εr is mainly affected by the ionic polarizability, lattice and bond energy, while P-O bond plays a decisive role in Q×f and τf value. Optimum properties of Q×f ~ 153,500 GHz, εr ~ 7.13 and τf ~ −59 ppm/°C were achieved for the composition LiMg0.9Zn0.06Ni0.04PO4 sintered at 875 ℃ for 2 h. This set of properties makes these ceramics an excellent candidate for LTCC, wave-guide filters and antennas for 5 G/6 G communication applications.