The functionalization of the polypnictogen ligand complexes [Cp′′2Zr(η1:1‐E4)] (E=P (1 a), As (1 b); Cp′′=1,3‐di‐tertbutyl‐cyclopentadienyl) is focused to modify the features of the polypnictogen unit to explore new synthetic pathways for further transformations. The reaction behavior of 1 towards main group nucleophiles is investigated. The reaction of 1 a with tBuLi leads to the ionic product Li[Cp′′2Zr(η1:1‐P4tBu)] (2) where an organic group is attached to a bridgehead phosphorus atom of the butterfly unit. Further reactions of 2 with quenching electrophilic reagents enable the introduction of other substituents. Moreover, a condensation of 2 to [(Cp′′2Zr)2(μ,η1:1:1:1‐P8tBu2)] (3), containing a novel P8‐unit, has been observed. The reaction of 1 with LiNMe2 and LiCH2SiMe3 leads to a partial fragmentation of the E4 unit and the compounds [Cp′′2Zr(η2‐E3Nu)] (Nu=NMe2: E=P (6 a), As (6 b); Nu=CH2SiMe3: E=P (7 a), As (7 b)) are formed.