Mg(Zr0.05Ti0.95)O3 (MZrT) ceramics nanoparticles have been synthesized by polyol method for the first time. The phase evaluation of the MZrT nanoparticles was confirmed using thermo gravimetric analysis and the phase purity of the samples were analyzed using X‐ray diffraction and Raman spectroscopy. The transmission electron microscopy (TEM) images revealed the average particle size between 30 and 40 nm. The optical bandgap is in the range of 3.66‐3.82 eV and is attributed to the quantum confinement effect. Interestingly, the nanopowders sintered at 950°C for 3 hours exhibit the maximum density of 97.52% of the theoretical density which is attributed to the higher sintering velocity of the smaller particles. The obtained microstructure of the ceramics reveals porous free uniform microstructure with prominent grain boundaries. A best combination of microwave dielectric properties (εr ~18.04, Q × fo ~175 THz at 9.5 GHz) are obtained for MZrT ceramics sintered at 950°C for 3 hours. The non‐Debye‐like relaxation process is found to exist inside the sample confirmed by impedance spectroscopy. The AC conduction mechanism is explained on the basis of Correlated Barrier Hopping model. Thermal conductivity of the MZrT ceramics is found to be 10 W/mK. The obtained properties of MZrT ceramics are suitable for resonator, microwave integrated circuit and LTCC applications.