Bulk-phase polycrystalline La1−xBixFeO3(x= 0.1, 0.2, 0.3, 0.4, and 0.5) ceramics were prepared by citric sol-gel and sintering methods. The structural, morphological, and electrical properties of the resulting sol-gel solutions were investigated using various techniques. In an X-ray diffraction analysis, all samples crystallized in the orthorhombic structure with thePbnmspace group and showed an increase in lattice constant with increasing Bi content which was also confirmed by vibrational analysis. The sample surfaces and average grain sizes were examined by scanning electron microscopy. The grain distribution was non-uniform and the grain size increased with the increasing Bi content. The complex electrical conductivities and dielectric analyses of these materials were investigated as functions of frequency by impedance spectroscopy at various temperatures (75-200 °C). The frequency-dependent dielectric constant at each temperature increased with increasing Bi content. A Jonscher's power law analysis revealed that the AC and DC conductivities arose by completely different mechanisms. The temperature dependence and dielectric relaxation of the DC conductivity satisfied the Arrhenius law and decreased with increasing Bi content. The activation energy ranged from 0.20 to 0.45 eV and was similar in the conduction and relaxation mechanisms, indicating that both transport mechanisms were based on hopping phenomena. We believe that lowering the activation energy will help with the optimization of constituents as promising candidates in novel materials for future electrocatalysts.