Pentaphosphaferrocenes [CpR Fe(η5 -P5 )] (Cp*=η5 -C5 Me5 ) (A), Cp''=η5 -C5 H3 tBu2 -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 AgSbF6 . Adding rigid aromatic dinitriles ortho/meta/para-(NC)2 C6 H4 in a one-pot reaction between [CpR Fe(η5 -P5 )] and AgSbF6 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 C6 H4 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 X-ray diffraction.