The synthesis of a linear polymer that includes both P=N and P=S double bonds, and P-O and P-C single bonds is reported by using two different paths that involve deprotection reactions and the Staudinger reaction. The preparation of hyperbranched polymers made up of OC6H4P(Ph)2=N-P=S repeating units is also described. Five generations of dendrimers originating from the same building blocks were prepared. The characterisation of all these phosphorus-based macromolecular architectures (solution behaviour, size exclusion chromatography, intrinsic viscosity, thermal behaviour) revealed marked differences in their respective behaviour.