Crystal structures of boron-rich solids are characterized by boron atom arrangements that are quite diverse: chains, sheets, and a variety of polyhedra like octahedra, pentagonal bipyramids, cuboctahedra, and icosahedra are observed. Probing by electron energy-loss spectroscopy (EELS), these different structural features are mirrored by a pronounced variation of the energy loss nearedge fine structure (ELNES) of the B K ionization edges. For identification, characteristics of these fine structures can be used as socalled "coordination fingerprints", which is shown for solids like