Pentaphosphaferrocenes [Cp(R)Fe(eta(5)-P-5)] (Cp*=eta(5)-C5Me5) (A), Cp''=eta(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 AgSbF6. Adding rigid aromatic dinitriles ortho/meta/para-(NC)(2)C6H4 in a one-pot reaction between [Cp(R)Fe(eta(5)-P-5)] 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)C6H4 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.