The multiferroic compounds with chemical formula Bi1−xBaxFeO3 with x = 0.00, 0.05, 0.10, 0.15, 0.20, and 0.25 were synthesized by sol–gel route. Thermogravimetric and differential thermal analysis were performed on a pure BiFeO3 sample to know the required annealing temperature. Its structural, morphological, optical, electrical and dielectric properties were studied systematically by standard techniques. X-ray diffraction (XRD) and transmission electron microscopy techniques were employed to study the structure and phase, as well as the morphology of the samples respectively. The transition from the distorted rhombohedral perovskite (ABO3) to hexagonal crystal structure was revealed by XRD pattern with Ba2+ substitution having R3c space group. UV-visible absorption spectra show that the absorption edge shifts to lower wavelength with increasing Ba2+ concentration. DC electrical resistivity measurements revealed a linear decrease in resistivity carried out in the temperature range of 343–1073 K using a standard two probe method. The dielectric parameters such as dielectric constant (ε′) and loss tangent (tanδ) were measured at room temperature in the frequency range 50 Hz–5 MHz, which was found to decrease with increasing frequency.