We report a new family of nickel phosphinidene molecular clusters synthesized from the reaction of bis(1,5‐cyclooctadiene)nickel(0) ([Ni(cod)2]) with organocyclophosphine and trialkylphosphine. We found that [Ni(cod)2] cleaves the organocyclophosphine P−P bonds to generate phosphinidene groups, establishing the cyclic molecules as valuable precursors for making charge‐neutral molecular clusters passivated by two‐electron donor capping ligands. The formation of the cluster core structure is controlled by the bulkiness of the precursor and of the capping ligand. As a demonstration of this new cluster‐forming reaction, we describe three clusters with different core nuclearity and degree of ligation: Ni12(PMe)10(PEt3)8, Ni8(PMe)6(PMe3)8, and Ni8(PiPr)6(PMe3)6. In addition, we show that the larger cluster, Ni12(PMe)10(PEt3)8, can be used as a low temperature single‐source molecular precursor to the catalytically active nickel phosphide phase Ni2P.