The idealized rhombohedral unit cell of boron carbide is formed by a 12-atom icosahedron and a 3-atom linear chain. Phase transitions are second order and caused by the exchange of B and C sites or by vacancies in the structure. Nevertheless, the impact of such minimal structural changes on the properties can be significant. As the X-ray scattering cross sections of B and C atoms are very similar, the capability of X-ray fine structure investigation is restricted. Phonon spectroscopy helps closing this gap. Phase transitions known to date have been identified due to significant changes of properties: (1) The phase transition near the chemical composition B8C by clear change of the electronic structure; (2) The endothermic temperature-dependent phase transition at 712 K by the according change of specific heat; (3) The high-pressure phase transition at 33.2 GPa by the drastic change of optical appearance from opacity to transparency. These phase transitions affect IR- and Raman-active phonons and other solid-state properties. The phase transitions at B~8C and 712 K mean that a well-defined distorted structure is converted into another one each. In the high-pressure phase transition, an apparently well-defined distorted structure changes into a highly ordered one. In all these cases, the distribution of polar C atoms in the icosahedra plays a crucial role.