BiFeO3 epitaxial thin films fabricated by pulsed laser deposition on different scandate substrates were investigated by means of Raman spectroscopy. We observed periodic changes in Raman position, full width at half maximum and intensity for some phonon modes as a function of the azimuthal angle ϕ. Further analysis revealed the possibility to assign the so far controversial discussed Raman modes at low wavenumbers (<250 cm−1) through rotational Raman measurements at different azimuthal angles, which show high sensitivity to the aforementioned parameters. Furthermore, the ferroelectric/ferroelastic domain structure shown by piezo‐response force microscopy investigations of the samples was confirmed. Our results are supported by symmetry‐based calculations including the analysis of Raman scattering geometry as well as the dielectric function of BiFeO3 in the infrared range. Copyright © 2015 John Wiley & Sons, Ltd.