ABSTRACT The present work is a demonstration of improved electrical and optical properties of barium zirconium titanate ceramic modified by the addition of Europium, i.e. Ba(1–x)Eu2x/3Zr0.05Ti0.95O3 (x = 0.01, 0.02, 0.03, 0.04). The Rietveld refinement studies confirmed the formation of tetragonal phase in the samples. The scanning electron microscopy (SEM) images revealed a decrease in grain size with increasing Eu concentration. The dielectric constant, dielectric loss and TCC plots are drawn to study temperature and frequency dependence of the samples. The electric field-induced strain behavior has been studied for all the compositions of the synthesized ceramic at room temperature. Conduction mechanism in the samples as a function of frequency and temperature was studied with the help of AC conductivity data. Also, the effect of grain and grain boundaries are studied in term of Cole–Cole plots. Photoluminescence (PL) emission spectra were recorded upon excitation with a wavelength of 360 nm.