The reaction ofN-trimethylsilylphosphineimines, Me3SiN˭PR1R2R3(R1, R2, and R3=hydrocarbon or NMe2group) with the fluorophosphoranes, MePF4, PhPF4, and Me2PF3has furnished fluorophosphineiminophosphonium organofluorophosphates, involving the anions, [RPF5]−(R=Me, Ph) or [Me2PF4]−, respectively. The characterization of these salts by1H,19F, and31P n.m.r. spectroscopy is described. The n.m.r. parameters are discussed in terms of electronic structure. The2Jpp coupling constant was determined to be positive by triple resonance experiments on two of the compounds.