The synthesis and thermal redox chemistry of the first antimony (Sb)– and bismuth (Bi)–phosphaketene adducts are described. When diphenylpnictogen chloride [Ph₂PnCl (Pn = Sb or Bi)] is reacted with sodium 2-phosphaethynolate [Na[OCP]·(dioxane)_x], tetraphenyldipnictogen (Ph₂Pn–PnPh₂) compounds are produced, and an insoluble precipitate forms from solution. In contrast, when the N-heterocyclic carbene adduct (NHC)–PnPh₂Cl is combined with [Na[OCP]·(dioxane)_x], Sb– and Bi–phosphaketene complexes are isolated. Thus, NHC serves as an essential mediator for the reaction. Immediately after the formation of an intermediary pnictogen–phosphaketene NHC adduct [NHC–PnPh₂(PCO)], the NHC ligand transfers from the Pn center to the phosphaketene carbon atom, forming NHC–C(O)P-PnPh₂ [Pn = Sb (3) or Bi (4)]. In the solid state, 3 and 4 are dimeric with short intermolecular Pn–Pn interactions. When compounds 3 and 4 are heated in THF at 90 and 70 °C, respectively, the pnictogen center Pn^III is thermally reduced to Pn^II to form tetraphenyldipnictines (Ph₂Pn–PnPh₂) and an unusual bis-carbene-supported OCP salt, [(NHC)₂OCP][OCP] (5). The formation of compound 5 and Ph₂Pn–PnPh₂ from 3 or 4 is unique in comparison to the known thermal reactivity for group 14 carbene–phosphaketene complexes, further highlighting the diverse reactivity of [OCP]⁻ with main-group elements. All new compounds have been fully characterized by single-crystal X-ray diffraction, multinuclear NMR spectroscopy (¹H, ¹³C, and ³¹P), infrared spectroscopy, and elemental analysis (1, 2, and 5). The electronic structure of 5 and the mechanism of formation were investigated using density functional theory (DFT).