High-performance ceramics with chemical formula (Ni1/3Ta2/3)xTi1−xO2 with excellent dielectric properties are demonstrated. The dopants of Ni2+ and Ta5+ in TiO2 caused the formation of oxygen vacancies and free electrons. The (Ni1/3Ta2/3)xTi1−xO2 exhibited low loss tangent of 0.046 and a high dielectric permittivity of 3.5–4.5 × 104 with a very weak dependence on temperature (−60 to 200 °C). Broadband dielectric spectroscopy shows at least four dominant sources in the dielectric relaxation response in the temperature range of − 253–210 °C. DFT calculations indicate the formation of defect clusters, which are the largest contributors to the dielectric response, and these are found to be dominant even at temperatures down to − 253 °C. Both grain boundary and surface layer mechanisms in the ceramics contribute to the dielectric response at the relatively high temperatures. The sample–electrode contact effect associated with oxygen vacancy diffusion is dominant at high temperatures above 150 °C.