Slow diffusion reactions of the pentaphosphaferrocene Cp*Fe(η5‐P5) (Cp*=η5‐C5Me5 (1)) with CuX (X=Cl, Br, I) in different stoichiometric ratios and solvent mixtures result in the formation of one‐ and two‐dimensional polymeric compounds 2–6 with molecular formula {Cu(μ‐X)}{Cp*Fe(μ3,η5:η1:η1‐P5)}n (X=Cl (2 a), I (2′c)), {Cu(μ‐I)}{Cp*Fe(μ3,η5:η1:η1‐P5)}n (3), {CuX}{Cp*Fe(μ4,η5:η1:η1:η1‐P5)}n (X=Cl (4 a), Br (4 b), I (4 c), Br (4′b), I (4′c)), {Cu3(μ‐I)2(μ3‐I)}{Cp*Fe(μ5,η5:η1:η1:η1:η1‐P5)}n (5) and {Cu4(μ‐X)4(CH3CN)}{Cp*Fe(μ7,η5:η2:η1:η1:η1:η1:η1‐P5)}n (X=Cl (6 a), Br (6 b)), respectively. The polymeric compounds have been characterised by single‐crystal X‐ray diffraction analyses and, for selected examples, by magic angle spinning (MAS) NMR spectroscopy. The solid‐state structures demonstrate the versatile coordination modes of the cyclo‐P5 ligand of 1, extending from two to five coordinating phosphorus atoms in either σ or σ‐and‐π fashion. In compounds 2 a, 2′c and 3, two phosphorus atoms of 1 coordinate to copper atoms in a 1,2 coordination mode (2 a, 2′c) and an unprecedented 1,3 coordination mode (3) to form one‐dimensional polymers. Compounds 4 a–c, 4′b, 4′c and 5 represent two‐dimensional coordination polymers. In compounds 4, three phosphorus atoms coordinate to copper atoms in a 1,2,4 coordination mode, whereas in 5 the cyclo‐P5 ligand binds in an unprecedented 1,2,3,4 coordination mode. The crystal structures of 6 a,b display a tilted tube, in which all P atoms of the cyclo‐P5 ligand are coordinated to copper atoms in σ‐ and π‐bonding modes. The right tool for the job: Small changes in the reaction conditions of pentaphosphaferrocene with Cu halides have a decisive impact on the supramolecular self‐assembly process to form 1D and 2D polymers. The novel products have been systematically investigated using single‐crystal X‐ray structure analyses and high‐resolution 31P solid‐state NMR techniques including R‐TOBSY experiments (see figure).