Despite the fact that different metal tetrafluorophosphoranides, M [PF 4 ] (M = Cs, Ag, K), decompose readily, we successfully enhanced the stability of such species by the replacement of two fluorine atoms with electron withdrawing pentafluoroethyl groups. Thus, AgF adds to P(C 2 F 5 ) 2 F, yielding Ag[P(C 2 F 5 ) 2 F 2 ], which served as a starting material for the synthesis of mono-, bis-, and tris[difluorobis(pentafluoroethyl)phosphoranido]silver complexes. Addition of 2,2′-bipyridine allowed for the isolation of stable [Ag(bipy)-{P(C 2 F 5 ) 2 F 2 }], whereas the reaction with the chlorides [NMe 4 ]Cl and CoCl 2 afforded the bis-and trisphosphoranidoargentates, respectively. Altogether, the difluorobis(pentafluoroethyl)phosphoranido moiety serves as a novel, small, noncyclic phosphoranido ligand. It provided access to the first homoleptic phosphoranidometal complex, [Co(NCMe) 6 ][Ag{P(C 2 F 5 ) 2 F 2 } 3 ]•2MeCN, which itself features the unusual structural motif of an [AgX 3 ] 2− ion.