Lead-free ceramic with the stoichiometric composition of 0.5 mol% Eu:BaTiO3 (EBT) is prepared by following the conventional solid-state reaction method. Prepared EBT is sintered at 1250 °C for 4 h. X-ray diffraction (XRD) study confirms the formation of a single-phase cubic structure that belongs to Pm3m space group. Field emission scanning electron microscopy (FE-SEM) shows the homogenous grain growth throughout the sample and the average grain size is estimated to be ∼0.8 μm. The value of the band gap is estimated from diffuse reflectance spectra and found to be ∼3.24 eV for EBT ceramics. Wide range of frequency (100 Hz–5 MHz) and temperatures (room temperature-500 °C) dependent dielectric response suggest that prepared sample exhibits maximum dielectric constant (ε′) at low frequency and this increases with increasing temperature. The value ε′ varies from 1865 to 8581 for the temperature range 300–500 °C at 100 Hz. The sample shows strong dispersion at low frequency in its dielectric characteristics which is a temperature dependent phenomenon. The enhanced dielectric properties of EBT suggests the applicability of these materials in electronic components designed for harsh temperatures.