In recent decades, a wide variety of cage complexes and metal-organic polyhedra have been synthesized and investigated for their significance in coordination chemistry and hostguest interactions. In addition, coordination polymers (CPs) and metal-organic frameworks (MOFs) have been extensively explored through self-assembly based on coordination bonding. Notably, CPs and MOFs incorporating metal-organic polyhedra as integrated structural units have also been constructed. A wide range of bridging ligands has been employed for the construction of CPs and MOFs. In particular, polycyano anions of the type E(CN)n -(E = B, C, N) are highly versatile bridging ligands, also acting as counter anions in ionic liquids (ILs). Notably, various cyanoborate anions, including BR(CN)3 -and BR2(CN)2 -, have recently been synthesized and used in the development of various metal complexes, including mononuclear, polynuclear, and cage complexes, as well as CPs, representing an intriguing class in coordination and supramolecular chemistry.