Pentaphosphaferrocenes [Cp R Fe(η 5 -P 5 )] (Cp* = η 5 -C 5 Me 5 ) (A), Cp'' = η 5 -C 5 H 3 tBu 2 -1,3 (B)) are excellent building blocks for polymeric assemblies in supramolecular chemistry in combination with coinage metal salts of weakly coordinating anions such as AgSbF 6 . Adding rigid aromatic dinitriles ortho/meta/para-(NC) 2 C 6 H 4 in a one-pot reaction between [Cp R Fe(η 5 -P 5 )] and AgSbF 6 leads to various coordination polymers (CPs) by a three-component self-assembly. The sterical demand of the differently substituted cyclopentadiene ligands as well as the rigid constitution of the isomeric dinitriles (NC) 2 C 6 H 4 play a key role in the formation of the isolated CPs. All CPs were characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal Xray diffraction.