Phosphoraniminato complexes of cadmium [CdX(NPEt3)](4) {X = Cl (1), Br (2), I (3), [CdI(NPMe3)](4) (4)} are formed by the reaction of cadmium dihalides with silylated phosphoranimines Me3SiNPR3 (R = Me, Et) in the presence of a fluoride source, e.g. NaF, at elevated temperatures. High yields can be achieved when R = Et and X is a heavy halogen. The exocyclic bromo function in complex 2 can be replaced by reaction with organolithium reagents to give organocadmium compounds [CdMe(NPEt3)](4) (5) and [Cd(C2SiMe3)(NPEt3)](4) (6) in excellent yields. Complexes 1-6 consist of a [Cd4N4] heterocubane core in which the cadmium atoms are linked by mu(3)-N bridges of the phosphoraniminato ligand with the cubane angles being close to 90 degrees. The crystal structure of an unsymmetrical cubane [Cd4I4(OSiMe3)(NPEt3)(3)] (7) is reported, in which one of the phosphoraniminato moieties has been replaced by a silyloxy function. All complexes are colorless oxygen-and moisture-sensitive crystalline materials, the heterocubane structure of which has been shown by crystal structure determinations and is consistent with spectroscopic findings, including IR, NMR, and mass spectra.