Abstract: A series of different generation hyperbranched waterborne polyurethanes(HPU) was prepared successfully from toluene 2,4-diisocyanate (TDI), dimethylol propionic acid(DMPA) and diethanol amine(DEOA) via monomer coupling reaction. The highest yield of the HPUs was up to 91%. The HPU products(generation from 2 to 5) and the line waterborne polyurethane(LPU), which have a similar chemical component, were characterized by the FT-IR, NMR, thermo gravimetric analyzer(TG) and differential scanning calorimeter(DSC), respectively. The molecular weights of the HPUs were measured by triple-detectors GPC; FT-IR and 13C NMR results proved that the hyperbranched structure was synthesized successfully. TG results showed that different generation HPUs and LPU had a similar initial degradation temperature at about 200℃.But the HPUs and LPU had a different degradation course obviously.; DSC results showed that the Tg of HPUs were higher than LPU apparently, and with the increasing of the generation, the Tg of HPUs rose from 115.2℃ to 150.3℃. Comparing with the different generation HPUs with LPU mixed films, the gloss and hardness improve significantly.