<p>Multiferroics have attracted considerable interest in recent times due to their unique characteristics. These materials have coupling between the electric and magnetic orders (ME coupling) which leads to the additional degrees of freedom in device making. Unfortunately, the materials exhibiting this coupling are very rare. BiFeO₃ (BFO) is one such material at room temperature. Here in this report, we emphasize on Bi_1 − xRE_xFeO₃ [<i>x</i> = 0.05, RE = La Ho, Dy] type materials synthesized by solid state route. These materials were characterized with Xray diffraction technique to establish the crystal structure acquired by the samples. The results were verified via Rietveld refinement technique. In addition to structural studies, the samples were examined for electrical properties using frequency dependent dielectric and Polarization (P-E loop) studies. For their use in optoelectronic applications, optical bandgap study using DRS UV-Vis spectroscopic technique was employed. The samples have been found to crystalize in trigonal (R3c) phase. The dielectric constant is witnessed better with lower dielectric dissipation property. The estimated optical bandgap is approximately 2e. the slight variations may have arisen from nature of dopants and size of crystallite. Due to their conducting nature, the materials display leakage behavior in P-E loop measurements. Overall, the samples are better dielectric, ferroelectric and opto-electric materials which need special attention for better performance.</p>