Our investigations using low-temperature Raman spectroscopy, dielectric, and magnetodielectric studies of as-prepared and vacuum-annealed BiFeO 3 ceramics revealed two dielectric anomalies near 25 and 281 K. Systematic studies were carried out to probe the anomaly near 25 K which exhibits clear frequency dependence and falls close to a previously observed magnetic transition. The low-temperature dielectric relaxation behavior yielded characteristic energy scales of ∼30 and ∼34 meV for the as-prepared and vacuum-annealed BiFeO3 samples, respectively. Raman spectra showed hardening of the E(TO6) and E(TO9) modes near 25 K, and the Raman shift in phonon frequencies is found to be broader in the vacuum-annealed BiFeO 3 than in the as-prepared BiFeO3. We observed a linear magnetodielectric coupling in both samples at 25 K. These experimental results suggest that coupling among spin, lattice, and dielectric properties persist to low temperatures in BiFeO3. © 2011 American Institute of Physics.