Waterborne polyurethanes (WPUs) with different mass ratios of soft and hard segments were synthesized by toluene diisocyanate, polypropylene glycol (PPG) and ethylene glycol (EG). It was shown that the PPG-based WPU with a mass ratio of soft and hard segments of 3:2 expressed a highest thermal conductivity (similar to 0.374 W/m.K), but showed a lowest T-peel strength (21.55 N/25 mm). As the mass ratio of soft and hard segments increased to 4:1, the T-peel strength was increased to 136.14 N/25 mm and thermal conductivity was decreased to a lowest value (similar to 0.306 W/m.K). To gain more understandings a number of analytic were carried out, such as FTIR, TG, DSC, DMA, AFM and XRD. Furthermore, mechanical properties of the PPG-based WPU coatings were tested as well. A possible explanation for the change in properties is due to the degree of phase separation and crystallinity, which was increased with the increasing of hard segment content. As a result, the hard and soft segments formed orderly oriented stacked structures by owing to the increasing of phase separation.