This paper reports the synthesis of Zn0.8Mg0.2TiO3 with V2O5 addition by means solid state-reaction method and their dielectric properties. Effects of sintering temperature with V2O5 addition on properties Zn0.8Mg0.2TiO3 such as appearances structure, microstructure, and dielectric properties have been investigated. Single-phase Zn0.8Mg0.2TiO3 was obtained by calcination of mixed raw materials, MgO, ZnO, and TiO2 at 800(for 2 hours. Sintering studies were carried out on samples with additive 2% mole V2O5 (ZMTV) and without additive 2% mole V2O5 (ZMT). X-ray diffraction analysis showed that the high sintering temperature provokes a formation of TiO2, ZnO, and Zn2TiO4 as minor phases. Microstructures analysis show that the V2O5 during sintering cause grain growth as indicated by SEM image. Dielectric characterization shows ZMTV sintered at 1000°C possesses the highest dielectric constant approximately ϵr ∼ 26. However, ZMTV showed higher loss tan δ especially in the space charge dipole at low frequency.