The appropriate pressure sensitive adhesion performances at working temperature are vital for the applications of waterborne polyurethane (WPU). Understanding the relationship among rheological behaviors, macromolecular structures and adhesive performances can be very useful to the rational design of waterborne polyurethane pressure sensitive adhesives (WPU-PSAs) for different operating temperatures, as well as other kinds of adhesives. In this study, four kinds of WPU-PSAs were prepared by reacting polypropylene glycol (PPG), hydrogenated hydroxyl-terminated polybutadiene (HHTPB), dimethyl alcohol propionic acid (DMPA), 1,6-hexamethylene diisocyanate (HDI) and four kinds of chain extenders. Gel permeation chromatography (GPC), swelling and rheology tests were used in parallel with an analysis of adhesive performances of the dried films of the adhesives. Results showed that, in addition to the nature of chain extenders playing a role on the rheological behaviors and adhesive performances of polymer, the gel content could be used to adjust the macromolecular structure and molecular weight distribution of polymer, thus distinctly affected the adhesive performances of PSA. The relationship among rheological behaviors, macromolecular structure and adhesive performances was investigated, and the rational design of WPU was achieved with appropriate pressure sensitive adhesion properties for different working temperatures of 25 and 60 °C.