Raman spectra of bismuth ferrite (BiFeO 3 ) over the frequency range of 100–1500 cm −1 have been systematically investigated with different excitation wavelengths. The intensities of the two-phonon modes are enhanced obviously under the excitation of 532 nm wavelength. This is attributed to the resonant behavior when incident laser energy closes to the intrinsic bandgap of BiFeO 3 . The Raman spectra of BiFeO 3 excited at 532 nm were measured over the temperature range from 77 to 678 K. Besides the abnormal changes of the peak position and the linewidth of the A 1 mode at 139 cm −1 , the prominent frequency shift, the line broadening and the decrease of the intensity for the two-phonon mode at 1250 cm −1 were observed as the temperature increased to Néel temperature ( T N ). All these results indicate the existence of strong spin–phonon coupling in BiFeO 3 .