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In this paper, the sol-gel technique has been employed to prepare the pure and TM (Mn, Cr) doped BiFeO₃ nanoparticles. The synthesized nanoparticles were characterized using X-ray diffraction, UV-vis spectroscopy, photoluminescence, and dielectric measurements. Crystal structural analysis infers that pure and TM-doped BiFeO₃ nanoparticles displayed a rhombohedral distorted perovskite structure with R3c space group, along with a minor phase of Bi₂Fe₄O₉. Lattice parameters have been found to decrease with TM doping. The particle size, measured with the help of the XRD spectra, was found to decrease from 54.4 nm to 38.7 nm with TM doping. The bandgap, determined using the UV-vis spectra, was observed to be 1.92, 1.66, and 1.54 eV for undoped, 5% Mn, and 5% Cr-doped BiFeO₃ nanoparticles, respectively. The dielectric constant shows a normal dispersion behavior at room temperature and its value increases with TM doping. The ac conductivity also increases with TM doping in BiFeO₃ nanoparticles.