Many of the fundamental questions regarding the solid-state chemistry of boron are still unsolved, more than 200 years after its discovery. Recently, theoretical work on the existence and stability of known and new modifications of the element combined with highpressure and high-temperature experiments have revealed new aspects. A lot has also happened over the last few years in the field of reactions between boron and main group elements. Binary compounds such as B6O, MgB2, LiB1-x, Na3B 20, and CaB6 have caused much excitement, but the electron-precise, colorless boride carbides Li2B12C 2, LiB13C2, and MgB12C2 as well as the graphite analogue BeB2C2 also deserve special attention. Physical properties such as hardness, superconductivity, neutron scattering length, and thermoelectricity have also made boron-rich compounds attractive to materials research and for applications. The greatest challenges to boron chemistry, however, are still the synthesis of monophasic products in macroscopic quantities and in the form of single crystals, the unequivocal identification and determination of crystal structures, and a thorough understanding of their electronic situation. Linked polyhedra are the dominating structural elements of the boron-rich compounds of the main group elements. In many cases, their structures can be derived from those that have been assigned to modifications of the element. Again, even these require a critical revision and discussion. © 2009 Wiley-VCH Verlag GmbH &. Co. KGaA.