A number of phosphoranimines were prepared via the Staudinger coupling of the suitably substituted phosphite with trimethylsilyl azide. These compounds were polymerized under various conditions using fluoride initiators and then characterized by H-1 and P-31 nuclear magnetic resonance, size exclusion chromatography vel sus polystyrene standards, and differential scanning calorimetry. The condensation by-products of the polymerization were analysed by gas chromatography-mass spectrometry. Mechanistic details of these polymerizations are also discussed. N-Blocked phosphoranimines were prepared and used as chain terminators to control the molecular weights of these polymers. Several random copolymers were produced by the simultaneous polymerization of two phosphoranimines, and the first reported block copolymers were synthesized by the homopolymerization of one monomer followed by the subsequent addition of a second. The synthesis of the first soluble aryl-substituted polyphosphazenes via the phosphine azide route is also discussed.