Different doping elements have been used to enhance the dielectric properties of BaTiO3ceramic. In this work, the effect of substitution of Ba by Bi in A site and Ti by Fe in B site on structural, dielectric and electrical properties of Ba1-xBixTi0.80Fe0·20O3ceramics at (x = 0.00, 0.05, 0.10 and 0.15) was investigated by X-ray diffraction, Raman spectroscopy, Scanning Electron Microscopy (SEM), Mössbauer spectroscopy as well as dielectric measurements. The Rietveld refinement results revealed that the prepared compounds crystallize in both tetragonal (P4mm) and hexagonal (P63/mmc) phases for x = 0.00 and 0.05 while at x = 0.10 and 0.15, the hexagonal phase disappears and only the tetragonal phase is fitted. The Raman spectra confirmed the disappearance of hexagonal phase in benefit of tetragonal phase as the Bi3+substitution increases. Based on Mössbauer analyses results, all the samples are in paramagnetic state at room temperature and the Fe is oxidized under Fe3+without the presence of Fe2+or Fe4+ions. The dielectric measurements as function of temperature are studied and tree broad and relaxor phase transitions were detected: from rhombohedral to orthorhombic phase TR-Oand to tetragonal ferroelectric phase TO-Tthen to cubic paraelectric phase Tm. These phase transitions were displaced to the lower temperature with increasing of Bi3+substitution. The values of ε′rincrease gradually with increasing of Bi3+contents which confirmed the enhancement of dielectric properties of BaTi0·80Fe0·20O3by Bi substitution on Ba site. The diffuse phase transitions were described by fitting the modified Uchino relation. The Cole–Cole analyses showed that both the grain and grain boundaries resistivity values are higher for Bi3+substituted samples which are responsible to the dielectric properties improvement.