The self-assembly of [Cp(Bn)Fe(η(5)-P5)] (Cp(Bn) = η(5)-C5(CH2Ph)5) with CuBr2 leads to the formation of an unprecedented rugby ball-shaped supramolecule consisting of 24 units of the pentaphosphaferrocene and an extended CuBr framework, which does not follow the fullerene topology. The resulting scaffold of 312 noncarbon atoms reveals three different coordination modes of the cyclo-P5 ligand including a novel π-coordination. The outer dimensions of 3.7 × 4.6 nm of the sphere approach the range of the size of proteins. With a value of 32.1 nm(3), it is 62 times larger in volume than a C60 molecule. Surprisingly, this giant rugby ball is also slightly soluble in CH2Cl2.