The first adducts of NHCs (=N‐heterocyclic carbenes) with aromatic polyphosphorus complexes are reported. The reactions of [Cp*Fe(η5‐P5)] (1) (Cp*=pentamethyl‐cyclopentadienyl) with IMe (=1,3,4,5‐tetramethylimidazolin‐2‐ylidene), IMes (=1,3‐bis(2,4,6‐trimethylphenyl)‐imidazolin‐2‐ylidene) and IDipp (=1,3‐bis(2,6‐diisopropylphenyl)‐imidazolin‐2‐ylidene) led to the corresponding neutral adducts which can be isolated in the solid state. However, in solution, they quickly undergo a dissociative equilibrium between the adduct and 1 including the corresponding NHC. The equilibrium is influenced by the bulkiness of the NHC. [Cp′′Ta(CO)2(η4‐P4)] (Cp′′=1,3‐di‐tert‐butylcyclopentadienyl) reacts with IMe under P atom abstraction to give an unprecedented cyclo‐P3‐containing anionic tantalum complex. DFT calculations shed light onto the energetics of the reaction pathways.