AbstractThe synthesis and characterization of a new series of polypropylenimine dendrimers is reported. Using a repetition of the sequence of a Michael addition to a primary amine, followed by a heterogeneously catalyzed hydrogenation, ultra‐pure polypropylenimine macromolecules with molecular weights up to 6912 are synthesized. The reaction sequence allows the preparation of these dendrimers at very large scales, whilst the availability of a simple purification in the sequence affords ultra‐pure samples. The polypropylenimine dendrimers are fully characterized; apart from the first 0.5 generation they are all oils, possess a Tg in the range from −90 to −40 °C, are unexpectedly stable, and their intrinsic viscosity drops after gene