AbstractAn in‐depth analysis of the description of bonding within Cp′′′Ni‐cyclo‐P₃ (Cp′′′=1,2,4‐tri‐tert‐butylcyclopentadienyl, [Ni]P₃) employing X‐ray diffraction based multipolar modeling, density functional theory (DFT) as well as an “experimental wavefunction” obtained from X‐ray restrained wavefunction (XRW) fitting is presented. The results are compared to DFT calculations on white phosphorus – an isolobal analogue to [Ni]P₃. A complementary bonding analysis shows insights into the reactivity of [Ni]P₃. The isolobal principle is reflected in every aspect of our analysis and the employed methods seamlessly predict the differences in reactivity of [Ni]P₃ and P₄. Crystallographic modeling, solid‐state NMR, and DFT calculations describe the dynamic behavior of the cyclo‐P₃ unit in the title molecule.