The authors report the study of polarized Raman spectroscopy of multiferroic Bi ferrite (BiFeO3) from 81-273 K, using a ferroelec./ferroelastic single-domain crystal with an as-grown pseudocubic (pc) (100)pc-oriented surface, compared with (001)pc thin film, grown by pulsed laser deposition. The polarized Raman spectra of the single crystal taken at different crystallog. orientations agree with the rhombohedral crystal structure with C3v point group, whereas the (001)pc thin film shows monoclinic structure, contrary to the bulklike rhombohedral and tetragonal structures reported earlier, but consistent with the recent synchrotron radiation studies. Earlier Raman scattering measurements on single crystals violated theor. predictions. This may be due to mech. polishing, which allows forbidden E (LO) scattering. All of the different phonon vibrations (A1 and E modes) in the single crystal have unambiguously been assigned.