The Ce-Co-doped BiFeO 3 multiferroic, Bi 1−x Ce x Fe 1−x Co x O 3 (x = 0.00, 0.01, 0.03, and 0.05), has been prepared by a sol-gel auto-combustion method and analyzed through Raman spectroscopy, photoluminescence, and UV-visible spectroscopy. We have observed an anomalous intensity of the second-order Raman mode at ∼ 1260 cm −1 in pure BFO and suppressed intensity in doped samples, which indicates the presence of spin two-phonon coupling in these samples. The photoluminescence spectra show reduction in the intensity of emission with the increasing dopant concentration, which indicates the high charge separation efficiency. A sharp absorption with three charge transfer (C-T) and two d-d transitions are shown by UV-visible spectra in the visible region. The band gap of BiFeO 3 (BFO) is decreasing with increasing dopant concentrations and the materials are suitable for photovoltaic applications.