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This study examines the use of tetrahedral [E(O-C6X4-CN)4]- anions (E = B, Al; X = H, F), which can be synthesized from the reaction of tetrahedral NaBH4/LiAlH4 and HO-C6X4-CN, as anionic linkers for the generation of 2D and 3D crystalline coordination polymer networks. Such polymer networks were obtained by the connection of tetrahedral p-cyanophenoxy aluminate or borate linkers with monocationic metal centers such as Li+, Na+, Ag+, and Cu+. These studies are specifically focused on the synthesis, structure, and stability of such polymers. Additionally, the perfluorinated O-C6F4-CN linker was used to study electronic influences. Salts bearing the perfluorinated [E(O-C6F4-CN)4]- anion decompose into E(O-C6F4-CN)3 and [O-C6F4-CN]-, which is also observed when a Lewis acid such as B(C6F5)3 is added. Moreover, addition of B(C6F5)3 leads to the formation of molecular-ion pairs because the cyano groups are now either completely or partly blocked. The structures of M[Al(O-C6H4-CN)4] (M = Li, Ag, Cu), Na[B(O-C6H4-CN)4], and Li[Al(O-C6F4-CN)4] as well as of the decomposition products Na(O-C6F4-CN), (THF)Al[O-C6H4-CN ·B(C6F5)3]3 (THF = tetrahydrofuran), Na[(F5C6)3B ·O-C6H4-CN ·B(C6F5)3], and Li[NC-C6F4-O-Al{O-C6F4-CN ·B(C6F5)3}3] are discussed. [ABSTRACT FROM AUTHOR]