In this research article, structural (crystal structure, micro structure) and electrical (dielectric, impedance and conductivity) properties of BaSnO3 (BSn) and BaSeO3 (BSe) modified (Bi0·5K0.5) TiO3 ceramic (i.e., (1–2x)((Bi0·5K0.5)TiO3)+xBaSnO3+xBaSeO3 with x = 0, 0.05, 0.10, 0.15 (BKT-BSn-BSe) have been fabricated via a high-temperature cost effective mixed oxide reaction process. The structural, micro structural and electrical characteristics of the parent compound ((Bi0·5K0.5) TiO3) have significantly been influenced by the substitution of BSn–BSe (in equal ratio) in it over a high temperature (100–500 °C) and frequency (1 kHz–1 MHz) range. Structural analysis of the compounds, carried out by the room temperature X-ray diffraction (XRD) data, confirms the formation of single phase compounds with tetragonal structure. The surface morphology of the materials, exhibits the homogeneous distribution of grains (with few voids) throughout the surface of the materials. The presence of bulk and grain boundary effect of the material is confirmed by the nature of Nyquist plot. J-E characteristics of the compounds show a negative temperature co-efficient of resistance (NTCR) behavior in them, similar to that of a semi-conductor. The ferroelectric phenomena of the prepared materials are studied by field dependence of polarization (PE) hysteresis loop study.